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By S. M. Purdy

Under certain conditions of hot rolling and air cooling from the hot-rolling temperature, bars of a high carbon (0.40 pct C) chrome-nickel austen-itic alloy were found to show magnetism even though no ferrite or martensite could be detected by microscopic or X-yay methods. The appearance of magnetism in such alloys may come from chromium impoverishment of the austenite grains near the precipitated carbide particles. SPORADICALLY, hot-rolled bars of Silchrome 10, an exhaust valve steel, have been found to be magnetic. Because of the analysis of the alloy—0.40 pct C, 18 pct Cr, 8 pct Ni, 3 pct Si —magnetism is unexpected. Preliminary investigation showed neither martensite nor ferrite to be present; only austenite and Cr23C6. Since a literature search was fruitless, a brief study was made of the appearance of magnetism in this alloy. The only basic difference between the two heats is the nitrogen content. Permeability was measured using a Severn magnetic gauge. This instrument consists of a magnet mounted on a counterbalanced arm. A set of calibrated plugs is placed in contact with one pole of the magnet. The specimen is placed close to the other pole of the magnet. If the specimen pulls the magnet away from the plug, it has a permeability greater than that marked on the plug. This technique is swift and reproducible. Previous experience has shown that the permeabilities obtained corresponded to those obtained on a permeater with a field strength of 100 oe. Specimens from both heats were annealed at temperatures between 1700 and 2300°F. One set of specimens was water cooled and another furnace cooled. All the water-quenched specimens were non-magnetic; the furnace cooled ones were magnetic as shown in Table I with no difference being observed between the two heats. Microstructural examination of the specimens showed the expected increase in carbon solubility with increasing temperature. Carbide solution was complete at 2200°F. The specimens heated to 1900°F or below showed some carbide precipitation from the hot-rolled structure. A furnace cooled specimen from a given temperature showed less carbide out of solution than the water-quenched specimen from the next temperature below; e.g., the specimen furnace cooled from 2100°F showed less carbide out of solution than the water-quenched specimen from 2000" F. These studies indicated that the appearance of magnetism was not related to the quantity of carbon in or out of solution and it was related to precipitation at temperatures below 1700" F. A set of samples annealed and water-quenched from 2100° F was aged for 4 hr at temperatures between 1000" and 1600°F; all were non-magnetic. A second set of samples, similarly annealed, was aged 1 to 24 hr at 1200°F with the results shown in Table II. None of the latter set of specimens showed magnetism until they had been aged about 8 hr. Magnetism was quite strong after aging 24 hr. X-ray diffraction studies on several of the magnetic specimens showed that the austenite had a lattice parameter of 3.58A and that the carbide was Cr23C6. Several of these samples were electrolytically digested in 10 pct HCl in ethanol, with a current density of 0.1 amp per sq cm. None of the particles in the residue were magnetic. Accidentally, one cell was run at 1 amp per sq cm; e.g., magnetic particles were found in this residue. After careful separation, the magnetic particles were mounted on a quartz fiber and their diffraction pattern determined using a 5.73-in. Debye-Sherrer camera with CrK radiation. These particles showed a fcc structure with a lattice parameter of 3.57A. Prolonged exposure, up to 16 hr, produced no other lines on the film. The following facts seemed to be established at this time: 1) Austenite was the magnetic phase. 2) Neither ferrite nor martensite could be detected. 3) Magnetization could be produced by aging at 1200°F. One explanation of these data is that the carbide precipitation impoverishes the region immediately around the carbide particle of carbon and chromium and increases the proportion of nickel. All of these serve to increase the Curie temperature of the region around the carbide particle. If the composition change is enough, the Curie temperature will rise above room temperature. If the volume of the affected region is great enough, the magnetism will become detectable. At low aging temperatures, composition changes are great enough but the overall volume of impoverishment is quite small

Jan 1, 1962

By B. D. Cullity, O. P. Puri

The magnetostrictia of nickel after increasing amounts of plastic elongation was measured at field strengths up to 1500 oe. In addition, the residual stress was measured by means of X-ray line shifts. The observed decrease in magnetostriction following plastic strain is shown to be associated with residual compressive stress. If a metal bar, whose longitudinal axis is taken as the x direction, is plastically elongated in the x direction and then unloaded, X-ray diffraction measurements will indicate the presence of a residual compressive macrostress 0%. However, stress measurement by means of mechanical relaxation does not reveal any macrostress. In a previous paper1 the fictitious macrostress indicated by X-rays was ascribed to a particular distribution of micro-stress, namely, one in which the bulk of the material was stressed more or less uniformly in compression and a very small portion in tension. It was shown that this distribution would account for Neurath's measurements2 of magnetic losses in silicon steel, because of the effect of residual stress on magnetostriction. The present paper is concerned directly with magnetostriction, in nickel, and with the effect on magnetostriction of the residual stress created by plastic elongation. The residual stress was determined by measurements of X-ray line shifts. MATERIAL AND METHODS Commercially pure "A" nickel was investigated. Its nominal composition, in weight percent, is 99.4 Ni + Co, 0.2 Mn, 0.15 Fe, 0.1 Cu, 0.1 C, 0.05 Si, and 0.005 S. Magnetostriction was measured by means of SR-4 electrical-resistance strain gages mounted on specimens 1/4 in. sq and 8 in. long. Magnetic fields up to about 1500 ce were provided by a multilayer, non-cooled solenoid. A considerable amount of heat was developed at the higher field strengths, and, to avoid errors due to changes in the specimen temperature, the following procedure was adopted. Each measurement of the magnetostriction X at a particular field strength H was preceded by demagnetization and an adjustment of the strain indicator to zero; the field H was then quickly switched on and the strain read immediately. Curves of ? vs H were flat for field strengths above about 750 oe for all specimens, and this constant value of X was accordingly taken as the saturation magnetostriction ?s The X-ray measurements of residual stress were made with a Norelco diffractometer on specimens cut from flat bars 1 1/4 in. wide, 1/8 in. thick, and 12 in. long. These measurements were confined to lattice planes parallel to the surface of the specimen. Two reflections were studied: the 311 CrKß line at 28 = 157 deg, and the 420 CuKal line at 28 = 155 deg. The line centers were determined by fitting a parabola to the peak of the line, as suggested by Ogilvie3 and as modified by Koistinen and Marburger.4 The CuKa doublet from the plastically elongated specimens was first resolved by the Rachinger method5. All X-ray measurements were made by counting at fixed angular positions. RESULTS The results of the magnetostriction measurements are shown in Fig. 1 and Table 1. The magnitude of

Jan 1, 1963

By J. Gordon Parr, L. P. Srivastava

DUWEZ1 has shown that pure titanium and pure zirconium transform martensitically during rapid cooling at temperatures about 30° and 15°C re spectively below their To temperatures. Holden et al.2 determined M, temperatures of Ti-Cu alloys by a metallographic technique applied to isothermally treated samples. Their results, superposed on the McQuillan3 version of the partial Ti-Cu diagram are shown in Fig. 1. Sources of metals were: Titanium: Iodide bar; Foote Mineral Co. Ltd. Zirconium: Iodide bar; Foote Mineral Co. LM. Copper: Spectrographic Standard; Johnson Matthey and Co. Ltd. Alloys were prepared by levitation melting under argon to the following nominal compositions:* 0.5, Quenching, at rates to about 8000°C per sec, was performed by cooling in a stream of helium (99.999 pct pure) a 3/64 in. cube of material previously heated by a tungsten coil in a system operating at. 10-5 mm Hg. Cooling rates below 200°C per sec w were obtained by controlling the current to the heater coil. The specimen was supported on a 32 gage Pt, Pt-Rh thermocouple attached through a DC amplifier to an Edin magnetic oscillograph (Model 8082) with a maximum chart speed of 250 mm per sec. Transformation temperatures were read off the oscillograph charts at the location of the beginning of the thermal arrest. The same specimen was quenched several times, and all runs were repeated on new samples. Regular calibrations of the oscillograph against a potentiometer were made between quenching experiments. The criterion of martensite formation was the effect of surface rumpling. Previously polished samples that showed a rumpled surface after transformation are assumed to have undergone martens itic transformation: transformations of a diffusion type produce no surface disturbance, Figs. 2 and 3. Electrochemical measurements were made in a cell described elsewhere4 whose electrodes were the martensitic and the diffusion-transformed materials in the following electrolytes:

Jan 1, 1962

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-' and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.' An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

By I. A. Lesk

The various materials utilized in the construction of integrated circuits, and the resultant materials interfaces, are discussed with emphasis on a materials system that is compatible with all types of integrated circuits and minimizes the number of different interfaces. Problems with interfaces may originate in the silicon, on its surface, and between other materials within the integrated-circuit package independent of the silicon. ThE difference between integrated-circuit theory and practice may generally be spelled out in terms of the difficulties in fabricating a desired structure. There are, of course, problems in forming the requisite materials, of the necessary composition and geometry, where needed. A distinct class of problem, however, is associated with interfaces— generally between different materials, but occasionally between regions of the same material. We require that each interfacial system perform its proper electrical, mechanical, and thermal function, and do so in an unchanging manner with time under the most severe operating conditions. In a practical sense, we deal in nonideal systems, such that it is generally not possible to form an interface exactly the way it was intended, even if we allow for a knowledge of the practical limitations of the fabrication system. Another way of looking at this situation is to realize that, when we form a group of interfaces under apparently the same experimental conditions, there are often differences of important consequence between them. Very high-magnification pictures, such as are obtained by an electron microscope, reveal fine structure that often differs over the area of a given sample, as well as from sample to sample. Low-magnification pictures look better, but don't eliminate the problem. The trend towards integrated circuits, and away from circuits fabricated utilizing separate components, is very strong in many areas of electronics. A typical silicon monolithic integrated circuit, still in place in the wafer on which it was fabricated, is shown in Fig. 1. The increased reliability which is being experienced through the use of integrated circuits can, to a large extent, be credited to the reduced complexity of the interface system that is present in the electronic system. A glance at Fig. 1, however, with all of its epitaxial and diffused p-n junctions, and interconnect system, shows that interfaces have been far from eliminated. Fig. 2, depicting a schematic cross-sectional view of a (partial) typical integrated circuit, illustrates in detail the numerous interfaces that occur in this type of structure. Besides the individual circuit elements, there are interfaces for isolation, and, Fig. 3, even a crossover requires a series of interfaces. What has been accomplished, however, irrespective of whether or not the total number of interfaces in the circuit is increased or decreased, is that the variety of interfaces is very much reduced. This is because there are fewer materials involved. Since the expense incurred in an R & D program to improve reliability is pretty much directly proportional to the variety of interfaces involved, it is economically advisable to work with integrated circuits for highest reliability. That is not to say that circuits built using standard components could not be made as reliable as integrated circuits, but that the expense involved because of the more complex over-all interface system would be much greater. Although electronic performance utilizing integrated circuits with all silicon elements (i.e., transistors, diodes, resistors, capacitors) is adequate for many applications, there are numerous instances where thin-film passive elements must

Jan 1, 1965

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By N. J. Grant, Hans Brunner

ThE materials used in this investigation were furnished by the Aluminum Co. of America and consisted of high-purity alurhinum (99.995 pct) and two aluminum-magnesium alloys containing approximately 2 and 5 pct Mg. The compositions of these alloys are listed in Table I. The materials were received as hot rolled 3/8-in. diam rods and were made from the same heats as the materials which were previously used in this laboratory.'j3 The rods were cold swaged to 1/4-in. diam by 1 in. long, and then had two parallel flats machined over the gage length 0.085 in. apart. The test bars were annealed for 10 min at 700° F, and strained 1 pct in tension at room temperature. They were electropolished (80 pct acetic acid; 20 pct perchloric acid, 70 pct concentration) at a temperature of 60°F at approximately 20 v. A grid, transverse or square, spaced 0.2 mm apart, was impressed by rolling a fine threaded screw (128 threads per in.) across the flat surfaces. The depth of the grooves was less than 5 p. For final annealing and grain size control the specimens were enclosed in aluminum foil and sealed in Vycor tubes. Annealing conditions varied from 1 hr at 700° F to 5 days at 1050° F, depending on the alloy content, to give for most of the specimens a final grain size of about 1 mm. This treatment was followed by electropol-ishing as described above. For the test series presented in Figs. 4 and 5 round specimens were used instead of flat ones, and fine machining marks served as marker lines instead of the impressed grid lines. Electropolishing was omitted. The major advantage is that the spacing of the machining marks is only about 1 u as compared to the 200 u of the impressed grid lines, permitting higher precision in strain measurements. Unfortunately the strain annealing necessary for grain size control also resulted in some preferred orientation of the grains. The preferred orientation of three arbitrary specimens was measured by X-ray diffraction methods and the averaged results are shown in Fig. 1. The possible effects of the preferred orientation on the test results will be discussed later. The testing temperatures were 410°, 515", 725", and 940° F, with one exception in the case of the 5.1 pct Mg alloy. Since the solubility limit of this alloy is 520°F, a test temperature of 545°F was cho-se sen instead of 515°F. The selection of the test temperature was based on two considerations: 1) at 900°F and above, extensive grain boundary migration made it more difficult to measure grain boundary sliding; 2) at 400°F and below, there was so little grain boundary sliding that it was again difficult to make precise measurements. The stress was chosen to give a creep rate of approximately 2.7 pct per hr in connection with Figs. 2

Jan 1, 1961

By Charles A. Stickels, Edward E. Hucke

The dihedral angle, formed by the intersection of three interfaces, is often determined by measuring a sample of apparent angles of intersection seen on a random plane of polish, then comparing the exerimental distribution of angles to the distribution calculated by Harker and Parker. Statistical tests show that the latter distribution does not satisfactorily describe the population from which samples are drawn. It is concluded that the major reason for this discrepancy is the presence of a range of dihedral angles in all specimens. When reasonable care is used experimentally, random measuring error is unimportant. It is shown that measurements made on dispersed second-phase inclusions are subject to a systematic error depending on inclusion size, which can be minimized by using adequate magnification. A dihedral angle, calculated from a sample of observed angles as though a unique dihedral angle were present, is termed an "effective dihedral angle". Experience has shown that "effective dihedral angles'' are reproducible quantities, useful for characterizing samples. Methods of determining an "effective dihedral angle", establishing its reliability, and making comparisons between samples are discussed. THE authors have recently reported measurements of the dihedral angle formed by liquid-lead inclusions lying in nickel grain boundaries.' Di- hedral angles were measured by the statistical method first employed by Harker and parker2 and used subsequently by many other workers.3"8 Since a relatively high degree of accuracy was necessary in the authors' experiments, the reliability of this method of dihedral-angle measurement was examined. Briefly, this method of measuring dihedral angles is usually performed as follows. A multiphase alloy is prepared, equilibrated under conditions which allow sufficient interface mobility to establish equilibrium, quenched to room temperature, then prepared for metallographic examination. A large number of observed angles, formed by the traces of grain boundaries and/or interphase boundaries on the plane of polish, are measured at high magnification. If all orientations of interfaces in the specimen are equally probable, Harker and parker2 showed that the population of observed angles is described by a distribution function containing a single parameter, the dihedral angle, 8. certain properties of the population, e.g., the mode or median, have been calculated from this distribution function in terms of the dihedral angle.3, 9 Thus, if the mode or median of a sample is identified with the corresponding property of the population, a unique value for the dihedral angle is determined. One defect in this procedure lies in identifying the properties of a sample of observed angles with the properties of the population from which they are drawn. If one were to proceed in a more rigorous fashion, it would be necessary to find a function of sample properties which is an estimator of the dihedral angle. Then by determining the distribution function for the estimator one could set limits on the value of the dihedral angle. The most apparent obstacle to this straightforward approach is the complexity of the distribution function assumed to describe the population. In analytical form, the distribution function may be written:2, 10

Jan 1, 1964

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,'-!' other investigators have encountered difficulty with the method."'. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By C. S. Smith, L. Guttman

It is shown, from a study of geometric probabilities, that the average number of intercepts per unit length of a random line drawn through a three-dimensional structure is exactly half the true ratio of surface to volume. Since the surfaces can be internal or external, the area of grain boundary or of the interface between any two constituents in a micro-structure can be measured. Other metric relations are tabulated that may be of use in studies of the microstructure of polycrystalline, cellular, or particulate matter generally. IN many fields of scientific investigation the structure of cellular aggregates or random arrays of discrete particles imbedded in some matrix is observed on a two-dimensional section and inferences are drawn therefrom as to the real structure in three dimensions. The biologist's microtome slice, the petrologist's thin section, and the metallurgist's plane polished and etched sections are common examples, although the problem is a general one. Scientists have commonly limited their thinking to the same dimensionality as their structures, and the few attempts that have been strictly three-dimensional in character have been laborious and noteworthy. From a metallurgical standpoint it is often of considerable importance to know, in addition to the volume fraction of two or more components in an alloy, the amount of two-dimensional interface between crystals. Such grain boundaries (which may separate either two identical crystals differing only in orientation or two crystals differing in structure, and possibly also in orientation) have a determining factor upon the mechanical behavior. It is at these boundaries that melting commences, that stress-induced corrosion occurs, and that various precipitates (harmful or otherwise) first appear. The boundary is doubtless of equal importance in nonmetallic crystalline aggregates such as rocks, ceramics, and concrete, and the biologist is deeply concerned with the area of cellular membranes. Many synthetic cellular foams involve similar structural problems. The very term structure usually implies the presence of interfaces and a complete understanding of structure involves nothing but an analysis of the geometrical, metrical, and topological relations between the various interfaces (zero, one and two-dimensional) that exist in a three-dimensional structure. Even systems lacking sharp physical interfaces often have interrelated gradients of composition or velocity (as cored crystals or turbulence cells) in which a neutral surface can be treated as a two-dimensional interface. In an earlier paper by one of the authors' the question of cell shape was considered in terms of simple topological principles without regard to physical dimensions. The determination of the actual size of grains in two dimensions is carried out in a routine fashion in innumerable metallurgical laboratories (see, for example, the ASTM standard methods of grain size determination2), though this is done merely to check the uniformity of a product and has no relation to the actual three-dimensional shape or size of the grains. Some authors have discussed the three-dimensional problem but only on the basis of assumptions as to idealized grain shapes.:'-' Quantitative measurements of microstruc-tures to obtain the volumetric relations of various phases have been carried out by petrographers for many years and are of increasing popularity among metallurgists." The present paper will show how, on the basis of no assumptions other than randomness of sectioning (usually realizable in experiment), it is possible to learn a great deal about the three-dimensional structure. The relations to be derived will generally be used on random arrays of cells or other particles, although they are equally applicable to ordered arrays and even to isolated objects of complex shape provided that suitable random sections can be made. Total Area of Interfaces in a Sample Consider a typical microstructure of a single-phase polyerystalline metal, such as that shown pres- in Fig. 1. The plane cross section shown contains a network of lines which subdivides the area into two-dimensional cells. The lines, of course, represent merely the intersection of the two-dimensional plane of sectioning with the two-dimensional interfaces between adjacent three-dimensional cells. The structure also contains points at which two or more lines intersect: in three dimensions the points are, of course, lines. In the more general case there may be in three dimensions isolated particles surrounded by a single interface without contact with others, and both two and one-dimensional features which do not necessarily connect with others. On the two-dimensional section these will appear as areas delineated by a closed line (as at a and b, Fig. 2), as isolated lines

Jan 1, 1954

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By Hermann Schmalzried, Carl Wagner

UPON heating a metal oxide or sulfide in H2, first only oxygen or sulfur is removed from the surface. Thus the metal/nonmetal ratio in the oxide or sulfide increases and the thermodynamic activity of the metal increases accordingly. For the formation of metallic nuclei, a certain super saturation is necessary, i.e., the activity of the metal must become greater than unity. Once nuclei of the metal have been formed, the supersaturation is supposed to decrease. Even under steady-state conditions of a reduction process, however, the activity of the metal inside an oxide or sulfide phase must be greater than unity in order to have a driving force for the individual steps of the reduction process. As an example, consider the reduction of Ag2S with a high mobility of cations and electrons. As shown schematically in Fig. 1, the reduction process involves the following steps:' 1) sulfur removal along the entire Ag2S surface in form of H2S, 2) migration of Ag' ions and electrons from the Ag2S surface to nuclei of metallic silver, 3) transfer of Ag+ ions and electrons from the Ag2S phase to the metal. For a finite rate of step 3, the activity of silver in Ag2S next to the Ag2S-Ag interface must be greater than unity. Moreover, for a finite rate of step 2, the activity of silver at the gas-Ag2S interface must be still somewhat greater. Theoretical considerations lead to the tentative conclusion that at least under steady-state conditions the supersaturation will be rather low.' To test this conclusion, the average activity aAg of silver in a Ag2S tablet about 2 mm thick with a diameter of 5 mm was followed as a function of time by measuring the electromotive force E of the cell Pt I Ag | Agl I Ag2S I Pt where AgI is used as a solid electrolyte in which only Ag+ ions are mobile. The activity aAg is calculated as aAg=exp(-EF/RT) Since the diffusion coefficient for transport of silver in Ag2S is very high (- 3 . l0-2 sq cm per sec),3 the average activity aAg is representative for both the bulk and the surface of the Ag2S tablet. Experiments were conducted at about 400°C. The cell was surrounded by an aluminum block in order to secure a uniform temperature and to eliminate thermoelectric effects. With the help of a potentiometer, first a potential of 0.16 v was applied to the above cell in argon in order to obtain a well defined initial state with a Ag/S ratio close to 2.000.~ Then the cell was disconnected from the potentiometer and a gentle stream of H2 was passed along the Ag2S surface. In view of the removal of sulfur in form of H2S, the electromotive force E decreased within 20 to 30 min to zero corresponding to a Ag/S ratio of 2.003 and became negative, indicating a value of aAg> 1. A representative plot electromotive force E vs time is shown in Fig. 2. The minimum of the electromotive force characteristic of the onset of

Jan 1, 1963

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The technique of unidirectional solidification has been applied to the A1-AI3Ni and A1-CuAl2 ezltectic alloy systems; the controlled microstructure of A1-A3Ni consists of parallel A13Ni whiskers emhedded in an aluminum matrix while the Al-CuAl2, system solidifies as parallel alternate lamellae of aluminm and CuAl2. Mechanical tests (tension and flexure) have shown that the particle-matrix interface bond formed during unidirectional solidification allowes for efficient load transfer from the matrix to the reinforcing phase. Strength and fracture characterstics of the alloys were studied as a function of phase orientation; the tensile strength of controlled Al-Al3Ni samples was 43,000 psi (three times greater than that of as-cast specime~s). The strength of the Al-CIA2, cutectic was studied as a function of lamellae-flexure stress-axis orientation using a microbend apparatus. A twofold increase in outer fiber stress was observed as the lamellae were rotated from a position of no reinforcing (perpendicular to the stress axis) to one of maximum reinforcing (parallel to the stress axis), The brittle reinforcing constituent in each alloy (A13Ni and CuAl2) was observed to he the nucleating phase for fracture. It is to be concluded from this investigation that unidirectionally solidified eutectic alloys have a potential use as reinforcing coniposite) materials. In a recent review article, Chadwick1 has described the work of many investigators in the area of controlled solidification of binary eutectic alloys. Thus far, more than twenty eutectic alloys have been unidirectionally solidified to produce structures consisting of two phases in the form of alternating lamellae or as whiskers embedded within a continuous matrix; in either case, the phases are aligned parallel to the growth direction. In particular, Kraft and Albright2 have shown that the Al-CuA1, eutectic alloy exhibits a lamellar microstruc- ture as a result of unidirectional solidification while Lemkey, Hertzberg, and Ford3 have studied the A13Ni whisker-aluminum matrix morphology in the A1-A13Ni system. Whether these alloys could exhibit reinforcing behavior would have to depend upon the strength and volume fraction of the reinforcing phase (AI3Ni and CuA12) and the nature of the bond between the reinforcing phase and the matrix. Hertzberg and Kraft4 have shown that the interface bond between chromium whiskers and a copper matrix in unidirectionally solidified Cu-Cr is particularly good while Lemkey and Kraft5 have reported chromium-whisker tensile strengths in excess of 1,000,000 psi. However, with the chromium volume fraction being less than 2 pct, no reinforcing behavior was displayed by the Cu-Cr alloy.6 In view of the encouraging results concerning the good interfacial bond and high strength of the reinforcing phase in the Cu-Cr system and preliminary mechanical test data reported by Lemkey et al.3 for the A1-A13Ni system, the A1-CuA1, and A1-A13Ni eutectic alloys containing 50 and 10 vol pct, respectively, of the reinforcing phase give promise of possessing mechanical reinforcing behavior. Based on this premise, the objective of the investigation was to study the strength and fracture behavior exhibited by these anisotropic microstructures. EXPERIMENTAL PROCEDURE Controlled Solidification Procedure. An extensive description of the technique of unidirectional solidification has been presented elsewhere.' However, the pertinent details for each eutectic system studied are discussed below. Al-A13Ni System. Several master heats of this alloy were prepared by vacuum-induction melting in an A12O3crucible and casting in SiO2 mold or by induction melting in alumina crucibles under argon. The initial heats were prepared from 99.99 pct A1 and 99.99+ pct Ni, while later heats used 99.999+ pct A1 and 99.99+ pct Ni. Specimens of these master heats were unidirectionally solidified using induction and resistance heating sources and argon atmospheres at growth rates from 1.1 to 28.7 cm per hr. The thermal gradients in the liquid were controlled in the range of 26" to 36°C per cm for these runs. Al-CuA12 System. The master heat and controlled

Jan 1, 1965

By N. S. Stoloff, R. G. Davis

It is concluded from an X-ray stztdy that the formation of the hcp Mg3Cd superlattice is a nuclea-tion and growth reaction. A two-phase, ordered-plus-disordered, region is observed between 153" nnd 141"C. A maximum in the flow stress is observed both at temperature and in quenched specimens within the two-phase region. The peak arises fro112 the extra energy required to create antiphase boundary upon cutting the ordered regions. Hardening during isothermal annealing in Mg3Cd has been shown to be similar to the domain hardening in Cu3Au-type alloys in that up to the maximum the structure is ordered domains growing into a short range ordered matrix. The hardening is due to a combination of short range order strengthening and the strengthening produced when antiphase boundary has to be created. In a recent study1 of the effect of long-range order upon the mechanical properties and deformation modes of hcp Mg3Cd a comparison was made be- tween quenched (disordered) and slow-cooled (fully ordered) specimens. The most striking observations were that the disordered alloy yields at a much higher stress than the ordered alloy, and that there is a change in slip mode from primarily (_0001) ba_sal slip in the disordered state to (0001), {1010}, {1122}, and {l011} slip in the ordered state. The main purpose of the present work is to extend these observations to determine whether MgsCd exhibits a peak in flow stress at an intermediate degree of order, or at a critical domain size, as do other orderedstems. However, disagreement exists about the Mg3Cd order transformation with respect to: 1) the location of the critical temperature for order, 165°C or 153"~,' and 2) how the degree of order varies with temperature. Welber et a1.5 concluded from specific heat measurements that the formation of Mg3Cd is a second-order reaction with the degree of order a continuous function of temperature, while Moore and Raynor concluded that it is neither a first-order reaction, with the degree of order a discontinuous function of temperature, nor a second-order reaction. Consequently it was considered necessary to undertake an X-ray investigation into the change in degree of order and structure in the

Jan 1, 1964

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By R. M. Brick, J. T. Richards

Tests have been conducted to determine the mechanical properties of several beryllium copper alloys down to liquid air temperatures. The materials investigated include beryllium copper, beryl-lium-cobalt-copper, and beryllium-zinc-copper in the wrought and cast conditions. As a means of evaluation, the influence of cold work and age hardening treatment upon subzero behavior has been observed. The effects of temperature upon both elastic and plastic deformation are also considered. THE low temperature mechanical properties of beryllium copper are of current interest in view of the increasing number of subzero applications. At extremely low temperatures, beryllium copper components are employed in temperature control and gas liquefaction equipment. At more moderate temperatures, such as those encountered in arctic regions, these alloys find use in a wide range of civilian and military applications. Although several previous subzero investigations have included beryllium copper,'-' none have been complete with respect to test temperatures or materials employed. As indicated in Table I, the alloy: used by Colbeck and MacGillivray,1 Walle,2 and Kostenets' were nonstandard and were not representative of present commercial practice. In addition, Kostenets4 did not test age hardened specimens, while the temperature in the other investigations", "-' were not carried below —100°F. These tests, however, indicate that beryllium copper offers interesting possibilities in subzero atmospheres, since the increase in strength with decreasing temperature is not accompanied by a reduction in ductility or impact resistance. As a means of checking and extending this earlier work at subzero temperatures, an investigation was undertaken at the University of Pennsylvania. In addition to testing the standard 2 pct beryllium copper, other alloys were also considered in wrought and cast forms. Charpy impact and tension tests were included with particular emphasis on the elastic characteristics, since beryllium copper is frequently selected for its spring qualities. Nominal test temperatures were +80°, —75", —200°, and —300°F. Test Materials Wrought beryllium copper, beryllium-cobalt-copper, and beryllium-zinc-copper specimens were machined from 0.560 in. diameter rod. These alloys were tested in the solution treated, cold drawn, or age hardened conditions. In the case of solution treated beryllium copper, some specimens were aged (3 hr at 600°F) for maximum hardness and others were overaged (1 1/2 hr at 750°F) to determine the effect of heat treatment. The compositions and average room temperature properties of these wrought alloys are presented in Table 11. The casting alloy versions of beryllium copper and beryllium-cobalt-copper were prepared as sand-cast cylinders, roughly 3/4 in. diameter x 6 in. long. Test specimens were machined from these cylinders. Conditions tested included as cast as well as solution treated and age hardened. Table 111 lists compositional and room temperature property data for the cast alloys. Test Methods Tension tests were conducted on specimens having a 0.25 in. diameter reduced section over a 1 in. gage length. To insure axiality, specimens were loaded by means of hardened chains. The yield strength at 0.2 pct offset was obtained from autographically recorded stress-strain curves resulting from a spe-

Jan 1, 1955

By K. G. Wikle, W. W. Beaver

A general survey of the mechanical properties of commercially pure beryllium fabricated from powder by vacuum hot pressing and other consolidation methods is presented. The effect of fabrication method, grain size, strain rate, and directionality upon both room and elevated temperature tensile properties is reported. BERYLLIUM metal, in spite of its rather restricted use, has been the object of attention for many researchers in the past half century. However, such work was performed on special experimental lots of metal made in small quantities by a variety of reduction methods. Not until 1946 was there a substantial production of beryllium metal, and not until 1950 was there a steady production of a commercially standard beryllium in the United States. This output was both the result of a requirement of the Atomic Energy Commission for a high grade beryllium of consistent quality and the development of a powder metallurgy process, by the Brush Beryllium Co., known originally as Process Q, which yielded a fine grained beryllium suitable for fabrication. Because this powder metallurgy product, known as QMV, superceded other types of metal made previously and represents the great majority of beryllium in use today, it seems worthwhile to present the results of studies on the mechanical properties of this metal as currently made. To the design engineer and the metallurgist, beryllium has extremely interesting properties. It is as light as magnesium alloys while having a stiffness modulus 40 pct greater than steel and a strength-weight ratio superior to titanium and aluminum alloys and aircraft steels. The melting point is high, 1287°C (2348°F), and it has good corrosion resistance both in air and water. Also, it is highly transparent to X-rays and has good heat and electrical conductivity (electric conductivity is greater than 40 pct of Cu). To the atomic energy program beryllium is considered a valuable material because of its low neutron-capture cross section and high neutron-scattering cross section which make it a good moderator and reflector for the lower velocity neutrons. A major technical difficulty limiting the use of beryllium, especially in structural applications, has been its notch sensitivity and consequent room temperature brittleness. Kaufmann, Gordon, and Lillie1 have reported their work on the mechanical properties of beryllium performed from 1946 to 1950. They studied the room and elevated temperature properties of cast and extruded beryllium and extruded electrolytic flake, Table I. Cast and extruded alloys of 85 to 99 pct Be were tested also. They found that extruded metal developed good strength and appreciable ductility in the extrusion direction and that thermal treatment and alloying provided little improvement in mechanical properties. They concluded that preferred orientation and fine grain size were the means of obtaining optimum tensile properties in beryllium. Other investigators have measured and commented on one of the most striking mechanical properties of beryllium, namely, its abnormally low Poisson's ratio.2 Udy, Shaw, and Boulger3 presented the latest published survey on properties of beryllium but their information is based only on published data available before April 1949 and cites little information on metal fabricated by powder metallurgy

Jan 1, 1955

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth, W. L. Finlay

Titanium with up to 7.5 pct Al forms single-phase a alloys that are work hardening, not heat treatable, and ductile as welded. The high aluminum Y phase alloys are not usefully ductile, despite their low hardness, but they have excellent oxidation resistance and hot hardness. LITTLE has been published on the effect of aluminum on the mechanical properties of titanium, despite the fact that two of the first four commercial alloys released by titanium alloy producers contained aluminum as an important alloying ingredient. These were both a-ß type alloys, one containing 4 pct A1 and 4 pct Mn and the other containing 3 pct A1 and 5 pct Cr. However, neither of these alloys reflects the true alloying nature of aluminum, since each contains important amounts of the ß-stabilizing addition, manganese or chromium. In a previous publication on the constitution of Ti-A1 alloys,' the authors showed that aluminum had a high solubility in a titanium and was strongly a stabilizing in nature. About 25 wt pct A1 is soluble in a titanium at room temperature. With as little as 5 pct added aluminum, the a transus temperature is increased from 882" to 970°C, and the correspond- ing ß transus to 995°C. The first intermediate phase in the Ti-A1 system is the ordered face-centered tetragonal TiAl phase, which extends from 34 to 46 wt pct Al. The present paper presents hardness data over the entire titanium-rich region of the system, through the TiAl phase, and mechanical property data on the alloy range capable of being fabricated. Methods of Investigation The materials used and general preparation of alloys, as well as experimental techniques used in the investigation of Ti-A1 alloys, have been adequately described.' Briefly, the preparation consisted of arc-melting the desired amount of high purity aluminum (99.99 pct purity) and iodide titanium (maximum hardness 100 Vickers, as deposited) together on a water-cooled copper hearth under a partial pressure of argon. The resulting button ingot was of such form that it could be fabricated without further treatment. All work was done using ingots weighing 10 to 15 g, which were hot-rolled to strip form whenever possible. Tensile samples were 3.25 in. long, 0.5 in. wide, and 0.040 in. thick, with a reduced section 1.25 in. long by 0.250 in. wide. The gage length used was 1 in. Electrical strain gages mounted on the

Jan 1, 1954

By Robert Lowrie

Nine intermetallic compounds were tested in tension at various temperatures. Seven exhibited extensive plastic deformation at elevated temperatures. Correlations of tensile strength and elongation are attempted with melting (decomposition) temperature, valence electron configurations of the component elements, heat of formation, crystal structure, density, and volume decrease accompanying compound formation. A LTHOUGH intermetallic compounds have been -tX known for many years, the study of their mechanical properties, particularly in tension, is just beginning. The problem has been unattractive because of the well-known, erratic behavior of brittle materials tested in tension. The strong influence of surface or internal flaws as stress raisers in non-ductile materials and the effect of eccentricity of loading in superimposing bending stresses on the state of tension in the specimen are extremely difficult to mitigate and impossible to completely eliminate. Thus, tensile properties determined for brittle materials, such as intermetallic compounds at temperatures low in comparison to their melting points, are at best only general guides to the values to be expected in an ideal test of a perfect specimen of the material. It is, nevertheless, surprising that apparently no attempt was made to follow up the pioneer work of Tammann and Dahl1 in this field. Working with crude apparatus, these investigators succeeded in showing unequivocally that at temperatures sufficiently close to their melting points (from 75" to 400°C for the compounds tested) intermetallic compounds did exhibit plasticity. This was indicated by the appearance of slip lines on the surface of the specimen. No observations of strength were made in these tests, which were of a compressive or indentation type. Rossi2 in 1932 attempted to study the physical and mechanical properties of single crystals of a group of intermetallic compounds. However, he was able to prepare only one material, Cu2Z8,, in the form of large, defect-free, single crystals. Thus, he was able to report only the relative fragility of the compounds at room temperature. He reported one compound, Ag,Zn,, to be somewhat plastic at room temperature and Cu,Si to be friable, the latter in agreement with results reported herein. Although test results are available only in classified literature, it has also been announced that MoSi, possesses some ductility at elevated temperatures." In 1948 and 1949 Savitskii and Savitskii and Baron -ublished their work on the hot extrusion of Mg-Zn, Al-Mg, and Cu-Zn compounds. Under the favorable state of stress existing for this process MgZn, MgZn,, MgZn,, ß (Al-Mg), ? (Al-Mg) and 0 (Cu-Zn) could be reduced by amounts up to 90 pct at elevated temperatures. These authors also report that hardnesses of Mg-Zn compounds decrease from room temperature values of about 300 kg per sq mm to 30 to 50 kg per sq mm at 325°C. They found that alloys consisting solely of one Mg-Zn compound were most resistant to softening on heating, mixtures of a compound and eutectic less resistant, and mixtures of two compounds least resistant. The more rapid softening of mixtures of

Jan 1, 1953

By W. L. Phillips

Nickel alloys containing approximately 0.5, 2.0, and 6.0 at. pct of Os, Pd, Ru, and Rh were Prepared by vacuum melting. Tension tests were carried out at 25°, 500°, 800°, and 1000°C; stress-rupture tests were carried out at 650° and 800°C. The room- and elevated-temperature tensile strength, as well as the stress-rupture life, increased for the same atomic percent in the order palladium, rhodium, ruthenium, osmium. The ductility decreased with increasing concentration or temperature for a given concentration. The results are discussed in terms of solid-solution theory. BOTH solid-solution strengthening and weakening have been observed in alloys. The simple rules which have been suggested to explain alloy strengthening are subject to several exceptions and deviations based on atom size and valency effects. The purpose of the present investigation was to extend the knowledge of the effect of solid-solution alloying on the mechanical properties of several Ni-Pt group metal alloys at room and elevated temperatures. The platinum group metals, osmium, ruthenium, rhodium, and palladium were chosen as the solute elements because of their different valencies and atom sizes. Nickel was chosen as the base material because of the large amount of previous literature available on nickel alloys. EXPERIMENTAL PROCEDURE Grade A Carbonyl nickel powder having the following composition: C, 0.07 pct; Fe, 0.013 pct; Mn, 0.0005 pct; Si, 0.016 pct; Mg, 0.0003 pct; S, 0.003 pct, was purchased from the International Nickel Co. The platinum-group metal powders were purchased from A. D. Mackay Co. The powders were weighed, cone-blended for 4 hr, and vacuum-melted into 1-in.-diam billets, approximately 2 in. long. The ingots were homogenized for 5 hr at 1800°F before being extruded into 1/4-in. rods at 2100°F. The alloy compositions are shown in Table I. Typical impurity values were not significantly different than that of the as-received nickel. All alloys were single phase. The lattice parameter of each alloy after the heat treatment described below is also included in Table I. Each alloy was annealed at 2200°F for 1 hr and air-quenched to comparable grain sizes (ASTM G.S. No. 4-5). The rods were then machined into test samples 0.160-in. diam and 0.750-in. gage length. Tension testing was carried out in an In-stron tension-testing machine at a strain rate of 0.02 in. per in. per min. An extensometer was used to determine the room-temperature yield stress. Stress-rupture testing was carried out in an Arc Weld stress-rupture unit. All testing was performed in air. EXPERIMENTAL RESULTS A) Room-Temperature Mechanical Properties. The 0.2 pct yield stress, ultimate tensile strength, and elongation for all alloys tested at room temperature are plotted as a function of atomic percent solute element in Fig. 1. The ultimate tensile strength for the same atomic percent increases in the order palladium, rhodium, ruthenium, osmium. The yield strength at low concentrations, -0.5 at. pct, increases in the order osmium, palladium, ruthenium, rhodium. At higher concentrations, 3.0 and 10.0 pct, the yield strength increases in the same order as the tensile strength. Both yield strength and tensile strength increase rapidly ini-

Jan 1, 1964