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By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct alloy content were carefully resolved. Phase relationships in the higher alloy content regions were outlined. A single intermediate phase, peritectically formed, of the form ZrX2 was established in each system. A eutectic and a eutectoid were found in the zirconium-rich region of both systems. Appreciable solubility of molybdenum and wolfram was found in ß zirconium, but only a slight solubility in a zirconium. PREVIOUS work on these systems was limited to X-ray investigations of the intermediate phases1, 2 and preliminary surveys of the zirconium-rich alloys." The diagrams presented were determined principally by metallographic, thermal analysis, and incipient melting techniques. In accordance with the Atomic Energy Commission contract requirements, phase relationships up to 50 atomic pct molybdenum or wolfram were carefully resolved, while only a limited amount of work was done to outline the 50 to 100 atomic pct alloy region. A description and analysis of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar, produced by the decomposition of a volatile iodide onto a hot filament, was employed for these studies. Westinghouse "Grade 3" crystal bar was used for all alloys. The zirconium, as received, was coated with corrosion product from a standard autoclave test by which its grade designation is determined. This was removed by a sand-blasting and HF-HNO, pickling technique developed by the Atomic Energy Commission. The bars were cold rolled to approximately 1/32 in. sheet, pickled for iron removal, sheared to 1/4 in. squares, washed with acetone, and stored for furnace charge. Molybdenum sheet. 0.003 in. thick, 0.001 to 0.005 in. wolfram wire, and M in. wolfram rod crushed to granular form, from Fansteel Metallurgical Corp., were used as alloying stock. Melting Procedure A nonconsumable electrode arc furnace identical to that described in detail by Hansen et al.4 was used. The source of power for melting Zr-Mo alloys was a 400 amp dc welding generator, while a 900 amp dc generator was used for preparing Zr-W alloys. Electrode tips of the same material as the alloy addition were employed in both systems, i.e., molybdenum tips were used for Zr-Mo alloys, and wolfram tips for Zr-W alloys. This precluded any possible electrode contamination during arc melting. Ingots of 20 to 30 g of Zr-Mo alloys were melted under high purity helium in the cavity of a copper block insert in a spun copper crucible. Homogeneity was insured by remelting all ingots four to six times without opening the furnace. Due to the large difference between the melting points of wolfram and zirconium, direct melting of the charged metals as above generally yielded ingots containing unmelted wolfram particles. This was overcome, after many variations in technique, by melting a pure wolfram charge at high power levels (700 to 900 amp) and slowly adding zirconium to form a master alloy. Such master alloys were sectioned and remelted several times, then crushed to serve as melting stock for alloys of lower wolfram content. Master alloys containing 26, 50, 52, 70, and

Jan 1, 1954

By R. W. Kraft

A back- reflection precession-type X-yay camera for determining the crystallographic orientation of the crystallites of both phases in small areas of thick specimens of polyphase alloys is described ad the geometry, advantages, and limitations of the apparatus are discussed. Metallographic obseg-vations of interfacial angles (or habit planes or growth direction are made on the same specimen so that the crystallographic and metallographzc orientation data call be directly correlated. An example of the application of tile technique to a unidi-~~ectionally solidified CuA12-A1 eutectic specimen is presented. The interfacial planes ad growth directions of each phase were established, and the orientation relationship between the phases was observed and found to be approximately intermediate between two previously reported relationships. The crystallographic interfacial relationship between two solid phases is an important parameter in a variety of metallurgical phenomena because of the energy associated with the interface and because this energy is at least partly associated with the way in which the two space lattices are in contact along the interface. In order to describe the interfacial planes in the crystallites of both phases it is necessary to determine the crystallographic orientation of each phase in a specimen relative to each other, and to directly correlate these data with met-allographic measurements from which the interfacial planes can be determined on the same specimen. The back-reflection Laue technique is the easiest way to determine the orientation of thick single crystals or large grains and the method can be combined with metallographic techniques to provide the necessary data, provided the reflections from each phase can be distinguished from one another. However, if the crystallites are small or of varying orientation or if one or both phases has a unit cell with less than the maximum symmetry, many overlapping and complex Laue patterns are recorded simultaneously and it becomes impractical if not impossible to interpret the photographs. All of these complexities were present in a unidirectionally so- lidified A1-CuA12 eutectic alloy1 for which a crystallographic analysis was desired. Consequently the method described here was developed since no known X-ray or electron diffraction technique had all of the following attributes which were required. 1) Method should yield data from which the crys-tallographic orientation of every crystallite or diffracting unit in the irradiated area can be determined. 2) Method should be adaptable to the study of small areas. Depending upon the degree of preferred orientation in the specimens, it should be possible to obtain reliable data in a reasonable length of time on irradiated areas as small as 1.0 or even 0.1 mm in diam. 3) Method should permit direct correlation of crystallographic data with microscopic orientation data pertaining to crystallite axes, habit, morphology, and growth directions as determined by optical microscopy. 4) method should be such that selected areas of large specimens can be easily studied. Trepanning of a small specimen (such as an electron microscope specimen) from larger specimens was undesirable since it would greatly increase the problem of correlating the crystallographic and microscopic directional data. Requirements 3 and 4 dictated that an X-ray back-reflection pinhole technique should be used on large samples, such as metallographic specimens which had previously been examined and analyzed for their microscopic characteristics. Similarly, requirement 2 could be satisfied by choosing a collimator of appropriately small diameter. Exposure times would not be excessive provided the detector were close enough to the specimen. Because of space limitations film was chosen in preference to a Geiger counter. Requirement 1 was fulfilled by using monochromatic radiation and providing enough additional degrees of freedom in specimen rotation to compensate for Bragg law restrictions on diffracted beams. DESCRIPTION OF APPARATUS The apparatus shown in Fig. 1 consists of a pin-hole collimator, (a), projecting through a rotatable circular film in a holder, (b), which records X-ray reflections in the back-reflection region. The specimen, (c), is mounted on the end of a shaft, (d), which is provided with an adjustment, (e), so that the specimen surface can be placed accurately on

Jan 1, 1962

By J. W. Rutter, K. T. Aust

The temperature dependence of the rate of grain boundary migration was measured in bicrystals of zone-refined lead containing from 20 to less than 1 ppm by wezght of tin. The apparent activation energy in the temperature range from 320" to 200oC is markedly dependent upon the solute tin concentration and upon the orientation relationship of the grains adjacent to the grain boundavy. The quantitative experimental observat~ons are compared with the predictions of various theories of grain boundary migration. In previous work.&apos;?&apos; the mobility of individual grain boundaries was studied as a function of impurity concentration and type of boundary. Grain boundary migration occurred at the expense of dislocation arrays which were introduced into the specimen during solidification. Boundary mobility in zone-refined lead at 300°C was markedly decreased by small additions of tin. 0.004 wt pct being sufficient to decrease the rate of grain boundary migration by a factor of 1000. The mobility of grain boundaries having polar orientation relationships near 38 and 22 deg about <Ill>, and 28 deg about <100>, was much less sensitive to tin concentration in the range studied. As a result, these boundaries have relatively high mobilities. The present paper is a continuation of the above study. Data are now presented on the temperature dependence of the motion of individual grain boundaries in zone-refined lead as a function of solute tin concentration and orientation relationship of adjacent grains at the grain boundary. The experimental observations are compared with the predictions of a number of theories of grain boundary migration3-8 which, prior to the present experimental investigation, could not be critically evaluated. EXPERIMENTAL PROCEDURE The striation or lineage structure of melt-grown single crystals of zone-refined lead, containing various additions of tin, was utilized to provide a driving force for grain boundary migration, as previously described.1,2 Each grain boundary under study separated the striated single crystal from another grain which was introduced by localized plastic deformation and recrystallization of a small region of the sample. The speed of migration of grain boundaries in dilute alloys of tin in zone-refined lead was investigated as a function of 1) tin concentration from < 0.0001 to 0.002 wt pct, 2) temperature in the range of 200" to 320°C, and 3) orientation relationship of the adjacent grains at the grain boundary. The substructure driving energy available for grain boundary migration was estimated to be about 4000 ergs per cu cm, within a factor of two, from specimen to specimen.&apos; The specimen dimensions, and growth and alloying procedures for the preparation of striated single crystals of lead of known tin composition, were as described previously.&apos; Each bicrystal was carefully wrapped in aluminum foil, and annealed in a well-stirred salt bath consisting of 50 pct NaNO2 and 50 pct KNO3, for known periods of time at a series of constant temperatures (*2°C). The grain boundary positions, before and after each anneal, were determined by etching lightly in a solution of 5 pct nitric acid in methyl alcohol, in order to follow the motion of the boundary and determine its rate of migration. Thus, the rate of motion of the grain boundary in a single specimen was measured at various temperatures. The above procedure was carried out for each grain boundary in seventeen different bicrystal specimens.

Jan 1, 1960

By J. C. Shyne, T. D. Gulden

The steady-state creep behavior, in compression, of indium containing a dispersion of atomized glass particles was studzed over a range of temperature, stress, and composition. The observed behavior was not consistent with a simple model of dislocation climb over dispersed particles. From room temperature to about 100°C the temperature dependence could be described by an activation energy about one and a half times that of self-dijfusion in indium while at higher temperatures a much higher ternperature dependence was observed. THE value of dispersion-hardened and precipitation-hardened alloys has long been recognized. The mechanism of hardening, however, is not completely understood, especially at elevated temperatures where dispersed particles increase creep resistance. Following the suggestion of Schoeck1 that the rate of creep in dispersion-hardened materials is controlled by dislocation climb over second-phase particles, Ansel and weertman2 derived steady-state creep equations for dispersion-hardened materials. Their derivation was based on dislocation climb over non-deformable spherical particles in a metallic matrix. For low stresses they predicted a linear relation between applied stress and steady-state creep rate. For stresses large enough to cause dislocations to pinch off around the precipitate particles, the theoretical creep rate was shown to be proportional to the fourth power of stress. For very high stresses an exponential stress dependence was predicted. In all cases the theoretical creep rate is linearly proportional to the diffusion coefficient. This provided the primary temperature-dependent factor. Subsequently, Ansel and Lenel3 reported some experimental data on SAP, a composite of aluminum and aluminum oxide, that was in good qualitative agreement with the above theories. Their experimental creep rates, however, were four orders of magnitude less than the theory predicts. This was attributed to a low density of active dislocation sources in the material; somehow the dispersed particles inactivated the dislocation sources instead of merely interferring with dislocation motion. Meyers and sherby4 have recently reported on the creep behavior of SAP. Their results were inconsistent with a simple dispersion-strengthening model and led them to conclude that a continuous network of oxide controls the high-temperature mechanical characteristics of SAP. Because of the rather complex mechanical behavior of SAP and the lack of agreement about the morphology of its oxide phase, it appeared desirable to study the creep of a dispersion-strengthened material of controlled morphology. For the present work a dispersion of spherical glass particles imbedded in a matrix of indium was chosen. The microstructure of this material was similar to the idealized uniform dispersion of hard spheres in a deforming matrix assumed by Ansel and Weertman in their theoretical treatment. SPECIMEN PREPARATION For experimental convenience, it was decided to use a low melting-point metal in this investigation. It was necessary that the metal not be oxidized readily up to its melting temperature and that it wet the second-phase particles. It was desired that the material chosen for the dispersed phase be available as a fine powder with closely controlled size and shape. The material chosen to satisfy these requirements consisted of a matrix of indium metal containing a dispersion of atomized particles of a soft soda-lime-silica glass ranging from 5 to 30 µ in diam. The glass particles had a highly regular spherical shape. The composite was made by stirring the glass powder into liquid indium maintained at a temperature just above the melting point of indium, 156°C. The creep specimens were prepared by a hot pressing operation. Five to ten g of the mixture were placed in a steel die and pressed at 125°C for 5 min under a pressure of 30,000 psi. The resulting specimens were cylinders about 3/8 in. in diam and ranged from 0.4 to 0.7 in. high. By following this procedure a uniform dispersion was obtained in the creep specimens. Typical microstructures of specimens containing twenty and forty volume percent glass powder are shown in Figs. 1 and 2. Unfortunately, grain size could not be determined by the metallo-graphic techniques used. CREEP TESTING PROCEDURE Creep tests were performed in compression under constant stress. The specimens were placed in

Jan 1, 1963

By R. R. Nash, W. F. Sheely, E. D. Levine

ThiS note reports on the variation with temperature of critical stress for basal slip of binary solid-solution single crystals of indium and of thorium in magnesium. PROCEDURE Alloy single crystal spheres were acid machined to 3/8-in. diam cylinders with the basal planes of the crystals normal to the cylinder axis and then annealed at 810°K. Stress was applied parallel to the slip system, (0001) [1120]. Experimental details will be presented in another paper.&apos; Two nearly equivalent&apos; techniques of stressing were used. Stress on the magnesium-indium alloy crystals was increased by 1 g per sq mm at 1-min intervals, and the critical flow stress was defined as the lowest stress to pro-

Jan 1, 1960

By J. H. Westbrook

UNTIL very recently the development of high temperature alloys has been strictly empirical. It is, in fact, a great tribute to the intuition, perseverance, and industry of the practicing metallurgists of this country and abroad that the amazing increases in gas turbine service temperature over the past 15 years have been achieved with so little fundamental knowledge. The result of this development has been the realization of successful but highly complex alloys possessing five, six, or more alloying elements and correspondingly complex microstructures. Within the last few years, considerable effort has been devoted to the identification of the secondary phases in these alloys and to the correlation of the presence or absence of such phases with alloy properties. Little attention, however, has been given the problem of identification of the mechanism (s) by which such phases enhance the properties of the alloy and especially to the assessment of the particular properties of the secondary phase (either in- trinsic or relative to the matrix phase) which are basically responsible for the improvement. Conceivable mechanisms which might apply include dispersion hardening and precipitation hardening. In both cases geometrical factors—particle size, dispersion, volume fraction, etc.—and agglomeration re-

Jan 1, 1958

By R. A. Bosch, F. V. Lenel, G. S. Ansell

RECENTLY, Ansell and aenel&apos; proposed a dislocation model to account for the yielding behavior of dispersion-strengthened alloys. The criterion for yielding used in this model was that yielding occurs when the shear stress due to arrays of piled-up dislocations fractures or plastically deforms the dispersed second-phase particles. Calculations based on this model predict that the yield strength, uysof a dispersion-strengthened alloy containing particles whose geometry permits them to be considered as straight, i.e. not curved, barriers to dislocations follows the relation where and are the shear moduli of the matrix and dispersed phase respectively, b is the Burger vector of a dislocation in the matrix, A is the mean free path between dispersed phase particles and C is a constant. This yield stress, ys, is closely approximated in polycrystalline alloys by the proportional limit. The offset yield stress, uoy, is the yield stress, uys, plus the increase of stress due to strain hardening in the offset strain increment. Previous investigation1 has shown that Eq. [I] describes the yielding behavior of several different dispersion-strengthened alloys as a function of the mean free path between dispersed phase particles at a constant temperature. The purpose of this investigation was to investigate the temperature dependence of the yielding behavior of dispersion-strengthened alloys. The alloys studied, MD2100 and MD5100, are SAP-type alloys containing flake shaped aluminum oxide particles dispersed in a matrix of commercial purity aluminum. The proportional limit and 0.2 pct offset stress of both of these alloys were determined as a function of temperature over the temperature range from -190" to 500 C. All tests were conducted on an Instron tensile testing machine. Stress was measured by means of the Instron load cell. Strain was measured by means of SR-4 strain gages attached to the tensile specimens. Stress sensitivity was 80 psi. Strain sensitivity was 2 x 10F Fig. 1 shows the values received for the proportional limit and 0.2 pct offset yield stress plotted as a function of homologous temperature for both the MD2100 and MD5100 alloys. Inspection of Eq. [I] shows that of the terms which determine the theoretically predicted yield stress, uy,, only the shear moduli have an appreciable temperature dependence. From Eq. [I] the yield stress at any temperature T, UT, may be predicted from the yield stress at any arbitrary reference temperature, in this case 25 OC, u25, by the relation where the subscripts T and 25 refer to the values of the property at test temperature and at 25"C, respectively. The temperature dependence of the yield stress predicted by Eq. 121, based on the observed value for the proportional limit at 25OC, is also shown in Fig. 1. In evaluating Eq. [2] the following data was used. The values for the shear modulus of

Jan 1, 1962

By W. G. Pfann

Under certain conditions, a molten zone can be made to move through a solid by impressing a stationary temperature gradient across the solid. This phenomenon can be utilized in fabricating semiconductive devices, growing single crystals, joining, boring fine holes in solids, measuring diffusivities in liquids, small scale alloying, and purification. Fundamentals and exemplary applications are outlined. ANEW aspect of the travel of a molten zone through a solid is considered in this paper. Whereas, in previously described zone melting techniques,&apos;-&apos; zones were usually caused to move by changing the position or temperature of a heat source, in the present technique a zone is made to move by impressing a temperature gradient across it. For example, a thin layer of molten A1-Si alloy, sandwiched between two silicon slabs having a temperature gradient normal to the layer, will travel through the hotter slab. One feature of temperature gradient zone melting, as this technique will be called here, is that zones of unusually small dimensions can be maintained. This leads to such diverse uses as have been listed in the abstract. In this paper fundamentals of the movement of a molten zone in a temperature gradient, and some practical applications thereof, are outlined. Assumptions The movement of a molten zone through a solid body of solvent substance in which a temperature gradient exists will be discussed. The length of the zone will be its dimension in the direction of motion. The direction of the temperature gradient will be toward the region of higher temperature. To be considered is a binary or higher order solute-solvent system in which the concentration of solute in the molten zone is sufficient to produce a lowering of the freezing temperature of the solvent which is at least of the order of the temperature range impressed on the charge. While we discuss primarily molten zones in a solid matrix, the principles are applicable to solid or vaporous zones in a solid matrix, a requirement being that the diffusivity in the zone be substantially greater than in the matrix. Diffusion of solute into the surrounding solid will be assumed negligible. In general, its presence will not basically alter the conclusions to be drawn. For illustration, a system represented by the partial constitutional diagram of Fig. la will be discussed, in which k, the distribution coefficient defined in the figure, is constant and less than unity. However, the technique is applicable to any solute- solvent system in which one component lowers the melting point of another component. Movement of a Molten Zone in a Temperature Gradient Consider, in the system AB of Fig. 1, where B is designated the solute and A the solvent, the effect of sandwiching a thin layer of solid B between blocks of solid A and placing the whole in a temperature gradient such that the temperature of the layer is above the lowest melting temperature of the system. Surrounded by an excess of A, the layer will dissolve A, becoming molten, and expand in length." As so- lution of A continues, at both interfaces, the mean solute concentration in the zone will move to the right in Fig. la, until at temperature T, the liquid at the cooler interface reaches the liquidus concentration C,. Solution of A thereupon ceases because the liquid T1 is saturated with A. The liquid at the hotter end of the zone, being at temperature T2, is not saturated with A at concentration C1. Hence solution of A continues there and concentration C2 is approached. A concentration gradient therefore is set up in the zone, causing A to diffuse toward the cool end and B toward the hot end. As a result, the liquid at the cool interface becomes supersaturated and a layer of crystalline A containing concentration kc, of B in solid solution freezes. Since a source of A

Jan 1, 1956

By A. Lawley S. Schuster

The tensile behavior of copper foils prepared from rolled bulk material has been studied over the thickness range 2 to 53 , and for a range of pain sizes. For foils of comparable grain size, having the cube texture and tested along (100), yield strength increases with decreasing foil thickness t below -26p, with a corresponding decrease in ductility. Deformation occurs in the form of localized slip clusters distributed throughout the gage section. To the extent that the tensile strength (10 to 18 kg mm-) is unaffected by foil thickness, and that the foils possess fair ductility, the stress-strain behavior resembles that of bulk material rather than that of whiskers or evaporated films of comparable dimensions. The dependence of yield strength o on foil thickness t below -26p is of the form: oy = oo + kt-1/2. Possible explanations for the stress increase are considered based on 1) the dependence of active dislocation source length on foil dimensions, 2) the locking of surface sources, or the blocking of mobile sources at the surface due to surface film. It is now well-established that filamentary whiskers of many materials show exceptionally high strength compared with bulk crystals.&apos;-11 As the diameter of the whiskers decreases to -1, the observed fracture strength approaches, and in certain cases exceeds, the calculated shear stress for the nucleation of slip in a perfect crystal.&apos; In general, the stress-strain curve is entirely elastic, with strains at fracture approaching 1 pct. Similarly, thin films12-24 of evaporated or electrodeposi-ted material have been shown to possess tensile strengths three to seven times that of bulk material, with total strains at fracture -1 to 2 pct. In the present study, attention has been directed to the room-temperature tensile behavior of thin foils of copper over the thickness range 2 to 53, prepared from rolled bulk material. Yield stress, ultimate tensile strength, elongation to fracture, and work-hardening behavior are measured as a function of grain size and foil thickness. Structurally such foils are superior to either evaporated or electrodeposited films, and in the recrystallized condition exhibit considerable ductility. Apart from preliminary work by Sumino and Yamamoto25 on the work-hardening behavior of rolled and recrystallized copper foils, no systematic tensile studies have been carried out on material of this form. EXPERIMENTAL PROCEDURE Tensile specimens were prepared from 99.995 pct purity rolled copper foils of thickness 2, 6, 12, 26, and 53, obtained from the Hamilton Watch Co., Lancaster, Pa. Irrespective of specimen shape, it is necessary to use tensile foils with edges free from notches or tears. To this end, any form of cutting operation was excluded, and the tensile foils prepared using a photoengraving process, the details of which are described elsewhere.26 Since tensile data are required under conditions of uni-axial stress, the specimen shape is extremely important. Ideally, the foil should be infinitely long, allowing a gradual taper from the grip area to the gage section; however, from a practical standpoint, long foils are easily damaged during testing. A modified tensile specimen was therefore selected having a parallel gage section 1.25 by 0.20 in. with a tapered shoulder section increasing to 0.5 in. at the grips, and an over-all length between grips of 4 in., Fig. 1. In practically all tests, these foils fractured within the parallel gage section. By approximating the foil contour (Fig. 1) to a hyperbola it is possible to analyze the stress distribution in the tensile foil using two-dimensional elasticity

Jan 1, 1964

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,&apos; Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6&apos;7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O&apos;Brien.&apos; The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O&apos;Brien&apos; is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,&apos; reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O&apos;Brien.&apos; Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By R. W. Guard, W. R. Hibbard

As part of a program to determine the deformation characteristics of pure metals, the tensile creep properties of high purity aluminum (99.994 pct Al) have been determined using a constant stress loading. The effects of prior annealing temperature, stress, and temperature were studied. These data have been examined on the basis of present-day theories. None of the methods was found to give an accurate representation of the data over all conditions studied. The structures of several specimens after creep were examined by optical and X-ray metallography. Marked changes in the grain size were found and it was substantiated that the magnitude of these changes was greatly influenced by the applied stress (or creep strain). The changes in fiber texture which occur on creep deformation are shown to be consistent with those observed on deformation at lower temperatures. UNDERSTANDING the properties of new mate-*-J rials under different experimental conditions must be based on considerable knowledge of the mechanisms involved in plastic flow and how to control them. Tension and creep tests have been carried out on a number of pure metals in order to document their deformation characteristics. It is hoped that a comparison of these data with theory will indicate those areas where work on mechanisms and their relation to metallurgical variables may be most fruitful. Since aluminum has often been used for studying the qualitative aspects of creep behavior, it was chosen for detailed study. The effects of annealing temperature, stress, and test temperature on the constant stress creep behavior were studied. Although most of the tests were made above one half the absolute melting temperature, a few tests were made at lower temperatures to give qualitative comparisons. Some specimens were examined metallo-graphically and by X-ray diffraction techniques after creep. Since only a limited number of specimens could be made from the available material, no effort was made to study detailed changes in sub-grain structure or other metallographic features. Servi and Grant3 nd Dushman et al.&apos; have previously published studies of high temperature creep of high purity aluminum. In both cases, a great deal of emphasis was placed on the minimum creep rate.

Jan 1, 1957

By R. P. Carreker

GERMANIUM is a member of that group of ele-nents—carbon, silicon, germanium, and tin-— that are currently of particular interest because of their interesting electrical properties. Near room temperature these materials of diamond cubic crystal structure are characteristically brittle. However, there have been several recent reports that germanium is not brittle at elevated temperatures These observations may be summarized as follows: 1—Germanium single crystals were observed to creep in bending under a maximum fiber stress of 6 kg per mm&apos; (8500 psi) at 500°C and above.&apos; The creep curves were sigmoidal, with an induction period that decreased with increasing temperature. 2—Germanium crystal bars have been bent 90" about radii ten times the bar thickness at 550°C.&apos; 3—-Audible clicks were heard when l/4 in. thick crystals were bent drastically at 450" to 500°C. No microstructural evidence of mechanical twinning was observed 4—Slip lines have been observed in tensile specimens deformed at 600°C, and are coincident with (111) planes, the close-packed planes of the diamond cubic structure.] The slip direction has not been established. 5—A germanium crystal has been compressed approximately 20 pct along a <110> axis at 700°C." The results reported subsequently were obtained in exploratory experiments intended to indicate some aspects of the behavior of germanium single crystals when tested in simple tension. Specimen Preparation A single crystal bar of n-type germanium was used. It was of purity corresponding to a resistance range of 2 to 20 ohm-cm. Tensile specimens were prepared by cutting small rectangular bars

Jan 1, 1957

By R. P. Carreker, R. W. Guard

True stress-true strain data are given for nominally pure molybdenum (99.95 pct) over the temperature range -196° to 1540°C (0.027 to 0.63 T/T). Strain rate sensitivity was determined by rate change tests and stress relaxation tests. Inhomogeneous yielding and strain aging effects were observed. The yield stress and tensile strength depend markedly on temperature below 400°C and are insensitive to temperature in the range 400&apos; to 800°C. The ductile to brittle transition range is +25O to -25OC. Strain rate sensitivity and stress relaxation effects are very large near room temperature. THIS report presents data which were obtained as a part of a continuing program designed to document the deformation behavior of nominally pure metals over a wide temperature range.&apos;" This research program is rooted in the conviction that sufficient tensile and creep data of appropriate quality and detail does not exist to provide precise phe-nomenological descriptions of the deformation behavior of pure metals as a function of temperature, strain rate, and grain size. Such knowledge is needed to provide a firm base for alloy design and an experimental framework to which theories of deformation must conform. These data also complement a parallel exploratory program investigating the properties of refractory metals, including molybdenum, and their alloys. Several important reviews and research reports dealing with the tensile properties of molybdenum as a function of temperature have appeared."-lo To a great extent the work to be reported in the present paper parallels that of Bechtold and of Pugh. The authors&apos; results are in general agreement with those of Bechtold and Pugh. The principle differences be- tween the present experiments and those published previously are as follows: 1—Wire specimens prepared from arc cast molybdenum were used in the present experiments, bar specimens were used by others. Pugh used arc cast material while Bechtold&apos;s most extensive results" were obtained on powder metallurgy specimens. 2—Several different grain sizes were tested in the present experiments. 3—The testing range was extended to cover from -196°C to 1570°C (0.027 to 0.63 T/Tm). 4—The combination of wire specimens, high speed autographic recording, and a stiff testing machine permitted more detailed study of initial yielding. The principle contribution of the present paper is the demonstration of the relatively consistent mechanical properties of nominally pure arc cast molybdenum specimens of differing metallurgical history. Bechtold and Scotts have shown that arc cast and powder metallurgy molybdenum samples have comparable tensile properties in the range —75" to 200°C when processed to have the same re-crystallized grain size. Material The molybdenum used in this investigation was supplied by the Climax Molybdenum CO. Its metallurgical history is outlined in Table I; the final products were 0,030 in, diam wire specimens annealed at 1100&apos; and 1375°C and 0.060 in. diam wire

Jan 1, 1957

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-&apos;" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.&apos; It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965

By H. C. Doepken

Wrought Hadfield steel was tested in axial tension at from 100° to —196°C, to determine flow and fracture stresses as well as conventional properties. Ductility and related properties, such as fracture stress, decreased continuously with temperature. Peculiarities during straining indicated possible martensite formation or mechanical twinning. THE mechanical properties of austenitic manganese steel have been summarized by Avery and Day,&apos; including the low temperature tensile properties reported by Hadfield and coworkers2,3 " These data show the material to be brittle at both liquid oxygen and liquid &apos;hydrogen temperatures. Avery and Day report considerable ductility measured by Charpy V-notch tests at —100°F (-73°C). Since the review of low temperature properties by Seigle and Brick&apos; show face-centered cubic structures, other than Hadfield steel, to be ductile at low temperatures, it was felt that a study of tensile properties, between the reported intervals, should show whether the decrease in ductility was a gradual decline or an abrupt drop beginning at some intermediate point. X-ray examinations were made in an attempt to shed further light on the mechanism of work hardening of austenitic manganese steel. The presence of a magnetic constituent has been found by Hall" and by Avery, Homerberg, and Cook." Krivobok7 demonstrated the growth of magnetic constituents on reheating cold-worked specimens. Hadfield2,3 &apos; and Goss found no a iron. The steel from which the specimens were taken was commercial hot rolled % in. diam rod of electric furnace steel. The ladle analysis was as follows: C, 1.40 pct: Mn, 12.11; P, 0.060; S, 0.012; Si, 0.120; Ni, 0.080; and Cr, 0.090. Fifteen specimens, 6 in. long, were cut from a

Jan 1, 1953

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

ALTHOUGH considerable effort has been devoted toward the determination of the mechanical properties of pure metals, it is extremely difficult to compare the results of such work. This is because of differences in method and type of test, grain size, heat treatment, and purity of material. There is very little information on the properties of most of the high melting point reactive metals with purities greater than 99.9 pct. Previous evidence concerning the tensile properties of unalloyed metals show that: body-centered-cubic metals are brittle at low temperatures; face-centered-cubic metals remain ductile; some hexagonal metals remain ductile, others become brittle. It may be that traces of impurities decrease the low temperature ductility of the body-centered-cubic lattice. This would suppose that a body-centered-cubic lattice free from impurities would exhibit nearly the same ductility as a face-centered-cubic structure. The present investigation has been an evaluation of the tensile properties of zone refined iron in order to determine whether higher purity material than that previously evaluated behaves differently. Experimental Procedure In this investigation, high purity iron was zone purified using the floating zone method.&apos; The starting stock was obtained from two sources. The first,

Jan 1, 1958

By A. J. Hatch

Recent disclosures concerning strengthening of anisotropic sheet materials under biaxial stresses are reviewed. This biaxial strengthening has been termed "texture hardening" by Backofen and is related to the normal anisotropy parameter, R. Measurements of R made on three annealed titanium alloys indicate a Ti-4Al alloy will have the greatest potential for texture hardening, followed in order by Ti-5Al-2.5Sn and Ti-6Al-4V. Relative to sheet texture, a review of the deformation mechanisms in titanium alloys would indicate that a preferred orientation for "texture hardening" is where the (0001) pole is normal to the sheet plane. This was confirmed by determination oj (0001) pole figures for the above three alloys. High R values are related to pole figures with (0001) normal to the sheet plane, whereas low R values are related to pole figures with (0001) split in the transverse direction from the sheet normal. PUBLISHED work by Backofen et al. 1 and Hosford and Backofen2 based on hill&apos;s&apos; mathematical theory of yielding in anisotropic metals has indicated that significant strength advantages under biaxial stresses are possible in hcp alloys, provided an ideal (0001) [1010] sheet texture exists. This tendency to strengthen under biaxial stresses has been termed "texture hardening".1 It can be quantita- tively characterized by a strain-ratio parameter, R, where R may be determined from the ratio of natural width strain to natural thickness strain as measured on a uniaxial test specimen cut parallel to the rolling direction. If R is greater than 1.0, then strengthening under biaxial tension would be predicted. Considering the a titanium alloys which have an hcp crystal structure, Williams and Eppelsheimer4 have reported that commercial-purity grades deviate from the ideal (0001) sheet texture mainly in an approximate 30-deg rotation of the basal plane, toward the transverse sheet direction. However, McHargue et a1.5 have shown that the angle of rotation of the basal plane is sensitive to alloy content. In particular, a titanium alloy with 3.8 pct Al was reported to have the ideal (0001) [1010] texture after cold rolling. Additionally, Backofen et a1.1 using plane-strain compression tests have reported R values greater than 5.0 for the commercial 0 alloy Ti-5A1-2.Sn (110-AT). In view of these findings, a program was initiated to further determine the potential of commercial Ti-5A1-2.5Sn and an experimental Ti-4A1 alloy with respect to "texture hardening". Also, because of its wide commercial use, Ti-6A1-4V was included in the investigation. BIAXIAL-STRESS THEORY FOR ANISOTROPIC MATERIALS Backofen ef al.,1 based on the mathematical theory of Hi11,3 has introduced the concept of "texture hardening". In this work, it was shown that possi-

Jan 1, 1965