Search Documents

By T. A. Read, H. K. Birnbaum

Deformation of AuCd alloys having the 8 (orthorhombic) and (3" (tetragonal) structures occurs by the stress induced motion of twin boutdaries. A restoring force acts on displaced twin boutdaries as a result of internal energy increases in the volume through which the boundaries are displaced. The phenomonology of the twin boundary motion is described and a mechanism for twin boundary motion and the restoring force is proposed. A time-dependent stabilization behavior of the twin boundaries, which is observed after the twins are formed by the diffusionless phase transformations, is described. THE AuCd 8 phase (ordered bcc structure) exhibits a transformation to a phase having an orthorhombic structure, 8' (space group D'), for compositions in the vicinity of 47.5 at. pct Cd and to a phase having a tetragonal structure, 8" (point group 4/m, m,m), for compositions in the vicinity 50.0 at. pct Cd. Both transformations are diffusionless, occur on cooling at 60" and 30OC, respectively, and are crystallo-graphically reversible.' They are accompanied by an inhomogeneous deformation which was observed to be twinning in the low-temperature phase. 3'4 The transformations may occur by a "single interface" or by "multiple interfaces."5'6 In the "single interface" transformation, the twinned product phase consisted of two twin orientations as shown in Fig. 1. In the multiple interface transformation the product phase contained "domains" each of which contained two twin orientations, Fig. 2. Deformation of specimens containing transformation twins was achieved by motion of the twin boundaries. Releasing the applied stress resulted in the displaced twin boundaries returning towards their initial positions. This "pseudo-elastic" behavior of the boundaries varied with time after the formation of the twin boundaries by the transformation.

Jan 1, 1961

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By Kichizo Niwa, Toshio Yokokawa, Mitsuo Shimoji, Yoshihiko Watanabe, Satoshi Kado

A LTHOUGH a systematic research on diffusion in liquid metals has not been carried out, partial studies have been developed by various workers in several systems. A few recent papers among them have shown that this line of approach is quite useful for understanding the structure of the liquid state. Furthermore, it has been found in kinetic

Jan 1, 1958

By David A. Thomas, John F. Peck

Fibrous microstructures and their development have been studied by metallography and by hardness and quantitative metallographic measurements. Thin, curved grains were observed in transverse sections of commercial tungsten wire and were developed in laboratory-drawn iron wire at reductions greater than about 70 pct. The unusual grain shapes are attributed to the nonuniform mode of deformation of the grains associated with the characteristic [I101 preferred orientation that develops in bcc metals during drawing. Transverse sections of heavily swaged iron wire showed a ospiral nebulao structure that appears to result from the elliptical shape of the cross section of the swaging dies and their rotary motion. Hardness and quantitative metallographic results show unusual trends that parallel the changes in microstructure. Other phenomena are considwed in light of the results, including the strength of fine wires of bcc metals, ocylindricalo textures, and the ductility of fibrous tungsten. 1 HE microstructure of tungsten wire in a longitudinal section shows grains highly elongated in the working direction, giving the appearance of a bundle of parallel fibers, Fig. l(a). Wires of tungsten and other bcc metals show a pronounced preferred orientation in which a [I101 direction is parallel to the wire axis.l The microstructure and texture of tungsten develop during warm working (working above room temperature but below the recrystallization temperature) into wire by swaging and drawing. Fibrous tungsten so produced has limited but useful room-temperature ductility, whereas annealed tungsten is brittle at room temperature. During an investigation of the effect of recovery annealing on the substructure of commerical 0.030 in. diam tungsten wire, it was found that transverse sections of the as-received material showed thin, curved grains, Fig. 1(b), instead of the expected equiaxed grains. The fact that Figs. l(a) and (b) show different sections of the same material at the same magnification is at first disconcerting, because the long dimension of the curved grains in the transverse section is several times the average fiber width in the longitudinal section. However, a longitudinal section cuts most of the curved grains across their narrow dimension, giving the appearance of a multitude of narrow fibers. On the other hand, the plane of a longitudinal section occasionally includes a long dimension of a curved grain, resulting in a broad ofibero, such as A in Fig. l(a). EXPERIMENTS AND RESULTS To investigate the origin of fibrous microstructures and particularly the unusual transverse-section structure of tungsten, rods of iron (also bcc) were drawn and swaged in the laboratory. One rod of annealed Ferrovac E was drawn in six steps to a total reduction in area of 87 pct (0.10 to 0.036 in. diam), and a second rod was swaged to the same reduction, using approximately the same reduction steps. Longitudinal and transverse sections of the swaged and drawn iron wires are shown in Fig. 2, for reductions in area of 39, 73, and 87 pct. A fibrous microstructure in longitudinal section is first evident at 73 pct reduction, and it is further developed at 87 pct reduction. The grains in transverse section remain equiaxed until about 73 pct reduction, when they become somewhat elongated and curved. At 87 pct reduction, the drawn wire shows thin, curved grains in the transverse section, similar to those observed in tungsten. The transverse sections of the iron wires swaged 83 and 87 pct reduction in area show the striking ospiral nebulao structure in Fig. 2(d). This struc-

Jan 1, 1962

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

By J. J. Pye, J. B. Drew

The surface-diffusion coefficients of Ni63 diffusing on low-index planes of nickel single crystals have been measured over the temperature range from 400° to 1000°C using a precision autoradio-gvaphic technique. The activation energy for sur -face diffusion appears to he the same on the {111}, {110), and (100) planes and amounts to -0.60 ev. This is in good agreement with the value (-0.62 ev) reported for (111) planes obtained by mass-transport techniques. In an earlier paper, the authors have reported self surface-diffusion coefficients on silver.' In that work, a deviation of the diffusion coefficients from linearity in the Arrhenius plot was observed at high temperatures. This effect was attributed to a loss of tracer atoms into the bulk by volume diffusion. The purpose of the present work was to extend the technique developed to the nickel surface-diffusion system up to the point where volume diffusion would come into play. The nickel system especially lends itself to this technique due to the high efficiency of the isotope in darkening the film and the large absorption of the weak radiation (0.063 mev /3- particle of the trapped tracer atoms. The diffusion coefficients and ictivation energy for different orientations on nickel can also be compared with a report published by Blakely and Mykura 2 where a mass-transfer technique was used. This paper reports the self surface diffusion of nickel on the low-index planes over a wide temperature range using a precision autoradiographic technique. EXPERIMENTAL PROCEDURE The experiment is similar to that described in the earlier publication consisting of a radioactive needle as a source resting on a flat, smooth, chemically polished surface annealed in a dynamic dry-hydrogen atmosphere. The needle is held snugly on the surface by a holder fabricated from commercially pure nickel. The point source is made by grinding down a small-diameter nickel rod until a tip of approximately 0.1 mm radius is formed. It is then etched and the needle tip plated with the radioactive isotope Ni63. Nickel single crystals were used whose main impurities were spectrographically determined as Co 0.05, Fe 0.007, C 0.005, and S 0.003 pct. The surfaces, oriented to within 1/2 deg of the low-index planes, were carefully mechanically polished and etched in a 50-30-10-10 hot solution of acetic, nitric, sulfuric, and phosphoric acids giving a smooth polished surface. The crystals were then washed in distilled water and alcohol. Annealing temperatures ranged from 400° to 1000°C with a furnace arrangement in which the crystals could be brought up to temperature in times short compared to diffusing times. The temperature was maintained constant to ±10°C. In the temperature range investigated, the ratio of the surface-diffusion coefficient to the volume-diffusion coefficient (Ds/Du) was 105 or more and the mean bulk-penetration values, calculated from literature values of volume-diffusion coefficients,3 were on the order of 10-5 cm. After the diffusion anneal, the sintered needle is removed, and both the radius of the needle point and spot left on the crystal face are measured. The crystal is then placed on photographic film. Diffusion profiles are obtained by scanning the film with a recording microdensitometer which has a slit width of 10µ. DISCUSSION AND RESULTS The experimental conditions are such that the source strength and needle radius are essentially constant and the time is adjusted such that the mean bulk penetration is small. An exactly analogous heat-flow problem has been considered by Carslaw and Jaeger4 and the solution can be written in integral form as:

Jan 1, 1964

By W. Rostoker, R. P. Elliott, B. W. Levincer

Phase equilibria in the Ti-Cr-Mo system have been investigated for alloys containing 100 to 40 pct Ti in the temperature range 550° to 1300°C. Five experimental isothermal sections and a surface of incipient melting are presented in addition to a summary projection of the space. Seven vertical sections have been constructed from the isothermal sections. A STUDY of the system Ti-Cr-Mo was undertaken as part of a program sponsored by Watertown Arsenal toward the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range contained by the titanium corner and the line of 64 pct Ti (all compositions are by weight) and the temperature range 550" to 1100°C. A surface of incipient melting was constructed from measurements on a large number of alloys. The system Ti-Cr has been established.&apos;-? The phase diagram is characterized by a wide miscibility field of the solid solution at elevated temperatures and a eutectoid reaction of the type: (15 pct Cr) + TiCr, (685C). The a solid solution has a very limited capacity for solution of chromium (< 0.5 pct Cr). The intermediate phase TiCr2 has at best a very narrow composition range. It has been shown that two allotropic modifications of this phase exist. However, this behavior does not appear to be perceptibly reflected in the form of phase boundaries of the type + TiCr,. In the system Ti-Mo,9-10 the phase is stabilized to successively lower temperatures with increasing molybdenum content. There are no known intermediate phases. The a solid solution is limited to less than 0.5 pct Mo. Because of the very extensive range of the phase, the ternary system was ideally suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." A parametric surface was constructed to provide the necessary basis for the application of this method. Preparation and Treatment of Alloys More than 60 alloy compositions were prepared for the study of this system. Alloy buttons of 10 grams were arc-melted in a nonconsumable electrode furnace using inert atmosphere protection and a water-cooled copper crucible. The construction and operation of this type of melting unit have been adequately described elsewhere.&apos;&apos; To insure complete solution of alloy additions, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" over the ingots. Iodide titanium (99.97 pct Ti) was used as the alloy base. An especially high quality chromium (99.9 pct Cr) was obtained from the National Research Corp. Molybdenum sheet (0.005 in.) of 99.9 pct purity was used.

Jan 1, 1954

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. 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 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 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 S. R. Goodman, Hsun Hu

The rolling texture transition in copper as a function of deformation temperature is found to be quite similar to that in high-purity silver. The ordinary copper type texture changes gradually to the brass type, accompanied by an increase in the stacking fault frequency, as the temperature of deformation decreases. The rolling textures obtained at low temperatures and the corresponding annealing textures compare remarkably well with the ordinary rolling and annealing textures of low-zinc brasses. Furthermore, it is also found that the observed stacking fault energies of copper specimens deformed at low temperatures correspond closely with those of low-zinc brasses, as deduced from measurements of the dislocation nodes. These results are consistent with the idea that texture transition may be significantly dependent on the stacking fault energy. It was shown in a series of previous publications1"3 that the rolling texture of high-purity silver changes gradually from the common silver type (or the brass type) to the copper type* with increasing temperature *The silver or brass type rolling textures are commonly described as (110)[112],4,5 whereas the copper type rolling textures are mainly (123) [a121 and (146)[211].5 Other ideal orientations have been used by various investigators for the copper type rolling textures, but the actual difference among these ideal orientations is rather small. of deformation, and that such texture transition can be correlated with the change in stacking fault frequency as a function of rolling temperature. Furthermore, it was shown that the formation of annealing textures in high-purity silver from the various rolling textures obtained during the course of texture transition depends entirely upon the deformation texture. From a common silver type or brass type rolling texture (such as produced by rolling at 0" or at 50° C) the recrystallization texture is mainly (120)[211], which is quite different from the recrystallization texture of brass.* However, for both ma- terials the orientation relationship between the rolling texture and the recrystallization texture can be expressed in terms of similar rotations around [Ill.] axes of approximately 30 or 35 deg. They differ in that the [Ill] rotational axes are different. In the case of high-purity silver, the axes of rotation are the two (111) poles near the plane normal of the deformed specimen with a (11l)[112] type rolling texture, whereas in brass, they are the (111) poles near the direction of rolling. For high-purity silver with a predominantly copper type rolling texture (such as produced by rolling at 150° or 200°C) the recrystallization texture is mainly (100)[001], or the cube texture, plus its twin orientations. It was shown previously6 that such reorientation observed in copper or aluminum can be described as [Ill] rotations of 30 to 40 deg. For intermediate cases, i.e., when the rolling textures are composed of a

Jan 1, 1963

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951

By R. W. Powers, M. V. Doyle

ThE solution of a diatomic gas such as 0, or N2 in a metal usually follows Sieverts&apos; law; i. e., Here C is the solute concentration at equilibrium and P, the gas pressure. The proportionality constant Ks is also the equilibrium constant for the reaction 1/2 02 (at pressure, P) - 0 (in solution at [21 concentration., C). to use oxygen as an illustrative gas. Sieverts&apos; law is therefore interpreted to indicate that diatomic gases go into metallic solution atomically and that the solute "gas" atoms interact negligibly with each other. Of course, this interpretation is strictly valid only over the temperature interval in which the reaction indicated in [Z] can be investigated. At temperatures several hundreds of degrees below this interval, the possibility of interactions between solute atoms is conceivable. Indeed, from internal-friction measurements some evidence for the existence of groupings of oxygen atoms in tantalum solid solutions was presented a few years ago.1,2 Over a range of solute concentration, the experimental oxygen internal-friction peak in tantalum, measured as a function of temperature at constant frequency of vibration, can be described as the sum of two elemental peaks, each corresponding to a separate relaxation process. At 0.7 cps, the height of the elemental peak found at 137°C is proportional to the oxygen content, whereas the height of the one at 162°C varies as the square of the oxygen concentration. The 137°C peak was presumed to arise from the stress-induced ordering of oxygen atoms among various classes of octahedral sites in the manner proposed by Snoek.3 The 162°C peak was attributed to a somewhat similar stress-induced ordering process, in which each oxygen atom was interacting with a neighboring oxygen atom. Similarly, the experimental peak due to nitrogen in tantalum can also be described as the sum of two peaks. The height of one varies as the nitrogen concentration and the other as the square of this quantity. In fact, some evidence of solute interactions exist for all oxygen and nitrogen solid solutions of Group V transition metals. However, the interaction energy was not obtained previously for any alloy. The determination of this quantity, as a part of a more intensive study of the interaction between oxygen atoms in solid solution in tantalum, is reported in this paper. PRINCIPLE OF THE EXPERIMENT Consider an equilibrium in a solid solution of tantalum between oxygen atoms which are bound together pairwise and those solute oxygen atoms which are not so associated. 20 (Ta) - O2 (Ta) [3]

Jan 1, 1960