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By Irving Cadoff, Richard Nolder

An analysis oj a series of samples of single -crystal silicon grown on sapphire shows that ,four distinct orientation relations exist. There are at least thirteen crystallographic planes which serve as substrates ,for epitaxial growth The model which assumes that silicon substitutes for aluminium and bonds with the oxygen atoms of the sapphire to form the first later for subsequent growth can account for the epitaxial geometry in all four cases. Multiplici-ties 01 specific orientations are found which are explained by the symmetry of both the sapphire and silicon crystal structures. It was reported in the previous paper' that single-crystal silicon films can be deposited on single-crystal a A1,03 (sapphire) with a wide variety of orientations. The silicon films, however, were found to deposit in only four different orientation relationships with respect to the sapphire substrate. The X-ray data have been analyzed to determine the plane and direction of atomic fit and an atomic model to account for the epitaxial relationships at the silicon-sapphire interface has been developed. These results are described in the present paper. EXPERIMENTAL The Laue X-ray data described in the previous paper were reduced to stereographic projections in a standard manner. These data were supplemented with X-ray reflection data obtained with -& E and A Full-Circle Goniometer (Electronics and Alloys, Inc.) mounted on a Phillips diffractometer unit. The silicon films were thin enough to result in characteristic reflections from the substrate as well as the silicon. The superimposed stereographic projections were analyzed to determine the orientation relationships. Ambiguities were resolved by referring to constructed models of various lattice planes for both silicon and sapphire. These lattice models were also used to develop the model for atom fit at the interface. DATA AND ANALYSIS 1) Crystal Structures. The crystallography of silico-n, which is of the diamond cubic class with a. = 5.4~, is straightforward. The sapphire structure is more complex and generally difficult to represent in pictorial form. It is of the rhombohedra1 class but usually referred to hexagonal axes. The transformation of indices between these two systems can lead to ambiguities which will have bearing on the analysis presented herein. Therefore, the basis used in this paper is described in the appendix. Referred to the hexagonal system, the parameters of sapphire are co = 12.95.&, a, = 4.75~, c/a = 2.73. All parameters are for room temperature. Figs. 1 and 2 illustrate schematically the hexagonal unit cell model of sapphire used for this analysis. The oxygen atoms are assumed to occupy positions in an idealized hexagonal array on basal planes. Their actual positions are in a slightly distorted hexagonal array. The aluminum-atom positions are scaled to their actual positions in the lattice with respect to the basal layers of oxygen atoms. It was found that an idealized model where the aluminum atoms are assumed to lie exactly at the octahedral interstices of the oxygen lattice, similar to that used by ~ronberg,' was not adequate for this study.

Jan 1, 1965

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By D. Turnbull, R. E. Cech

FISHER, Hollomon, and Turnbull have developed a theory for the nucleation of martensite. They first tested the theory on Fe-C alloys and low alloy steels. The major factor influencing nucleation of martensite was considered to be statistical composition fluctuations occurring in small regions at high temperature and frozen-in on quenching. These local regions of varying size and composition serve as nucleation centers. They become supercritical, one by one, as temperature is progressively lowered, resulting in temperature-dependent or athermal transformation. Fisher next applied nucleation theory to substi-tutional solid solution alloys. Detailed predictions were made for Fe-Ni alloys because of the availability of free energy data on this system. It was shown that composition fluctuations that were significant energy-wise did not occur, and nucleation frequencies could be calculated from average properties of the system. Nucleation was predicted to occur as time-dependent and having the functional relationship to give a C curve of nucleation frequency vs temperature. The analysis further predicted that the nucleation frequency was extremely sensitive to composition. Experimentally, it would be found that the transformation in some compositions is so slow that measurable amounts will not form in a reasonable length of time. With other compositions, only slightly different, the nucleation frequency becomes so great that the material becomes transformed while still distant in temperature from the maximum nucleation frequency. On quenching an alloy of such composition, the observed transformation kinetics would be similar to those found in Fe-C alloys. Cech and Hollomon repeated experiments of Kurdjumov n which the kinetics of transformation were similar to those predicted by Fisher for Fe-Ni alloys. The alloy studied in this investigation contained 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn. Fisher,' using an idealized model for the extent of transformation as a function of the number of martensite crystals per grain of parent phase, derived nucleation frequencies from the transformation curves of Cech and Hollomon. Complicating influences such as coupling effects between grains in the polycrystalline specimens were neglected. Nevertheless, excellent agreement was found between the theoretically and experimentally derived nucleation frequencies. These experiments, however, could not provide a critical test of the theory. Experimental nucleation frequencies could vary widely from those calculated, depending upon the extent of deviation from ideal partitioning and the extent of coupling effects. Further, since the compositions of material theoretically analyzed and experimentally determined were different, the free energy changes involved in the experimental work could only be estimated. Also, the effect of heterogeneities on the transformation kinetics was not considered. For these reasons, it was decided that experiments designed to test the validity of the Fisher analysis must be conducted on binary Fe-Ni alloys, which were the ones considered theoretically by Fisher. The martensite transformation in Fe-Ni alloys has been the subject of considerable study. Machlin and Cohen have shown that transformation proceeds in a manner quite unlike that in any other ferrous alloy system. They found that single crystals would transform to a large extent in a single burst. In large grain polycrystalline specimens, frequently more than one grain and sometimes the whole specimen would transform at the same instant in this manner. Results on filings indicated that different particles would undergo the burst transformation at widely different temperatures. These results support the conclusion that the transformation behavior could not be described by a single nucleation frequency as would be the case if the nucleation were homogeneous. It appeared that further work was necessary to define the factors responsible for burst-type transformation, so that the conditions could be altered to favor homogeneous nucleation of martensite if such could be accomplished. This report summarizes the results of some experiments conducted with powdered Fe-Ni alloys for this purpose and the re-

Jan 1, 1957

By M. J. Saarivirta

A high-purity copper-zirconium alloy system was imesti-gated. The zirconium content of the alloys studied varied from 0.003 to 0.23 pet. The solid solubility of zirconium in copper and some physical and mechanical properties of the alloys have been determined. By proper heat treatment, Cu-Zr alloy can develop a high electrical conductivity and resistance to softening at temperatures up to 500°C (930°F). This combination of desirable properties makes this alloy superior, to other com-merzcrrl copper base alloys for- use in the electrical conductor field. DEMAND for high conductivity copper alloys that retain their mechanical properties at elevated temperatures is growing rapidly. At present, copper-base alloys such as copper-silver and copper-chromium are used where these characteristics are required. As an example, commutators in electric motors are often made of these alloys. However, the life at elevated temperature of commutators made of copper-silver alloys is much shorter than the life of the same part made of copper-chromium and copper-zirconium alloys. Copper-silver alloys are subject to creep and subsequent failure when the service temperature exceeds several hundred degrees centigrade. Use of copper-chromium alloys has been known for the past several years, but little information is available in the literature concerning the properties of alloys in the copper-zirconium alloy system. Some work had been directed toward determining the solubility of zirconium in copper as well as determining properties of the Cu-Zr alloys. These investigations have revealed the superior high-temperature and electrical conductivity properties of copper-zirconium alloys over copper-chromium alloys. The United States Metals Refining Co., Carteret, N. J. has recently produced OFHC R copper-zirconium alloys for experimentation and evaluation. Because OFHC R copper contains no appreciable oxygen, no harmful oxides are formed and the full benefit of Zr as an alloying addition is obtained. This paper describes the results of this work. It contains room-temperature and some high-temperature data which have been obtained after various processing techniaues. Actual elevated temperature properties are being determined and will be reported in a separate paper. Preliminary results obtained at elevated temperatures suggest that the Cu-Zr alloy is superior to other high conductivity copper-base alloys. WORK PROCEDURE The high-purity oxygen free (OFHC R) copper-zirconium alloys with zirconium content ranging from 0.003 to 0.23 pct were cast into 4-by 4-in. wirebars by both continuous casting and conventional casting methods. Zr was added in the form of a master alloy containing 30 pct Zr and 70 pct Cu. Castings were analyzed for zirconium and nine bars containing various amounts of zirconium were selected for this study. The results of analyses and the sample numbers are given in Table I. Typical analyses of OFHC R copper are also shown. The following properties were studied: A) Solid solubility of zirconium in copper. B) Effect of zirconium on properties of copper. C) Effect of combined working and heat treating on properties of Cu-Zr alloys. The solid solubility of zirconium in copper was determined by metallographic techniques. Specimens for this phase of the investigation were hot rolled at 900oC (1650oF) to 0.250-in. rod. The rolled rods were cut into 2/3-in. long specimens and solution annealed at 950 °C (1740°F), 980°C (1795 °F). and 1020 °C (1870 °F) for 6 hr and quenched in water. In order to find the solid solubility limits at lower temperatures, the homogenized specimens were reheated at various temperatures for 1 hr and quenched. The physical and mechanical properties were determined on 0.250 in. rod, 0.132- and 0.081-in. wires. The wires were cold drawn from the 0.250-in. rods after they were solution annealed at 980 °C (1795°F) and quenched in cold water. Mechanical and electrical properties were determined on cold drawn and

Jan 1, 1961

By A. W. Cochardt

THERE are a number of effects that can cause material damping or internal friction. Some of these are frequency dependent, such as the thermo-elastic effect' and the stress-induced ordering.' Others depend on the amplitude of vibration, i.e., the damping related to the motion of dislocations3 and that due to magneto-mechanical hysteresis.' While many of these effects have been studied, only the magneto-mechanical effect has found extensive practical application. It is the principal source of damping in the current blade material in steam turbines.A magneto-mechanical hysteresis loop is seen in Fig. 1. If an unmagnetized, polycrystalline wire of a material exhibiting magneto-mechanical hysteresis, such as an Fe-14 pct A1 alloy, is twisted in torsion, a relation between shear stress and shear strain y is observed as indicated. The stress-strain curve does not follow Hooke's law -dashed line. Instead, the strain y increases nonlinearly and partly irreversibly, due to the motion of ferromagnetic domain walls,* until a critical stress is reached, which in this case is about 3,500 psi. If the applied stress is raised further, the strain appears to increase linearly and reversibly in accordance with Hooke's law, since all domains are now aligned in easy directions of magnetization nearest to the direction of the applied stress, and plastic flow has not yet started noticeably. On removing the applied stress, a remanent shear strain y, is observed, which is related to the irreversible magnetostriction of the material.' The energy dissipated in the material during a stress-strain cycle is proportional to the critical stress t, and the remanent magnetostrictive shear strain 7,. The purpose of this investigation was to make a survey of the magneto-mechanical damping of ferro-

Jan 1, 1957

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By R. H. Raring, F. E. Martin

A high speed gas quenching dilatometer useful in studying phase transformations in low alloy steels is described. Changes in specimen length are measured by means of an electrical micrometer tube. The maximum instantaneous cooling rate is approximately 5000°F per sec; the maximum average cooling rate from 1650' to 950°F is approximately 2900°F per sec. Data for steels of 0.11 pct and 0.67 pct C content are included. KNOWLEDGE of phase transformations as they occur in an alloy under conditions of continuous cooling affords valuable insight into its properties. The transformation characteristics during continuous cooling of steels of high hardenability, which decompose entirely to martensite at fairly slow cool-

Jan 1, 1957

By M. Cohen, D. Caplan

The scaling characteristics of three Fe-Cr alloys have been investigated by determining their weight gain vs. time curves at 1600° to 2000° F. The scales formed thereby have been examined using the techniques of X-ray diffraction and spectrographic and metal-lographic analyses in an attempt to explain the discontinuities in the curves and to elucidate the mechanism of scaling. DESPITE the considerable number of investigations that have been carried out on heat resistant alloys, the characteristics of the scales formed at high temperatures are not fully known. The research reported here was undertaken in an attempt to ascertain the mechanism of scaling of the stainless steels. Scaling experiments were carried out first, the weight increase of the specimens being followed continuously with time. It was observed that, as well as showing the expected decrease in oxidation rate with time, the oxidation curves showed breaks corresponding to intermediate periods of accelerated oxidation, after which protectiveness again increased. This phenomenon was observed with austenitic stainless steels (types 302, 309, and 330) and with Fe-Cr alloys (types 410, 430, and 446), but only the latter are treated in this report. An examination of the scales was made using the techniques of X-ray diffraction and spectrographic and metallographic analyses in an attempt to obtain a correlation between the nature of the scales and the oxidation curves. A search through the literature revealed only a very few previous reports of such periods of accelerated oxidation. Dunn' found breaks in the oxidation-time curves of some Cu-Si alloys but saw no rational explanation of the phenomenon. Heindlhofer and Larsen2 attributed a discontinuity in the weight gain-time curve of iron at 1290°F to the formation of blisters, the subsequent cracking of which exposed an unprotected surface and permitted rapid oxidation until a new protective scale had been reestablished. They advanced no explanation, however, for what they termed the peculiar behavior of a 27 pct Fe-Cr alloy at 2000°F which gained weight very rapidly in between two periods of very slow weight gain. Portevin, Pretet, and Jolivet3 in describing breaks in the weight gain-time curves of Fe-A1 alloys suggested that they might be associated with the occurrence of localized and deeply oxidized areas on the specimens. Bandel4 in a general discussion of oxidation curves of heat resistant alloys considered that the discontinuities were due to a local disruption of the protective layer by the growth of iron-rich oxides. Day and Smith" in their report on the scaling of a large number of iron alloys noted but did not explain occasional relatively rapid changes in oxidation rate at higher temperatures. Chevenard and Wache6 found breaks, often two per specimen, in the oxidation curves of an 18-8 type alloy. They suggested that the cause might be a depletion in chromium of the surface layer of metal due to its selective oxidation, the resultant high concentration of iron and nickel in the scale leading to a poorly protective scale. McCullough, Fontana, and Beck' explained the breaks in the oxidation curves of types 304, 430, and 410 alloys as due to mechanical ruptures. Experimental Work Table I lists the chemical compositions of the materials used. Cylindrical specimens 1/4 in. in diam and 11/2 in. long were machined from cold rolled % in. rod. After a fine finish cut with a sharp tool, the specimens were abraded while still mounted on the lathe with Nos. 2, 1, 0, and 00 metallographic grade emery papers. A 3/64 in. hole was drilled at a distance of 1/8 in. from one end to permit suspension in the furnace. Specimen Nos. 1, 2, and 3 were tested with this surface preparation. All others, after being similarly prepared, were electropolished in a perchloric-acetic electrolyte, electrical contact being made by pressing a tapered platinum hook into the drilled hole. The specimens were then washed in hot water, rinsed with distilled water, rinsed with methanol, dried at 120°F, and weighed. Thereafter,

Jan 1, 1953

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By S. F. Reiter, W. R. Hibbard

A survey of the effect of heat treatment on the room temperature hardness of Fe-Mo alloys has been made. Constant strain rate tensile tests were performed between room temperature and 1800°F. These data were analyzed to determine the effect of temperature and composition on the strain hardening coefficient and strain rate sensitivity. Constant load creep-rupture tests were made on these alloys and the results related to composition and structure. A relation between the high temperature strength of the precipitation hardened alloys and the volume of precipitate has been observed. IN view of the extensive use of ferritic materials at elevated temperatures, it is surprising to note the limited amount of information relating the variables of plastic deformation, i.e., composition, structure, temperature, stress, strain, and strain rate. Hollomon and Lubahn' showed how the several variables of plastic flow might be treated analytically. No data were available on carbon-free iron and its alloys in a form suitable for this analysis. Several German investigations2-" constitute most of the experimental work relating high temperature properties to the constitution of these types of materials. In order to obtain new data, the iron-rich alloys of the Fe-Mo system were selected for detailed investigation for the following reasons: 1—Some of the important effects of molybdenum on the mechanical properties of iron have already been studied.' , 821 2—By suitable heat treatment of selected alloys, it is possible to study strengthening effects of four types: AT -a transformation, B—substitutional, C—precipitation, and D—dispersion of hard inter-metallic compound. Materials and Treatment Four-pound ingots were vacuum cast, employing the same melting schedule previously used.? The raw materials were electrolytic iron and lamp-grade molybdenum. The ingots were forged to l/z in. sq. rod and one portion swaged to 0.350 in. diam rod for the production of 1 15/16 in. long button-head specimens. The button-head specimen blanks were solution treated for 16 hr at 2100°F in hydrogen of —70°C dewpoint and then water quenched. They were subsequently plunge ground to the standard 0.160 in. diam test bar. Micrographs of the solution treated alloys are given in Figs. la through Id. The higher molybdenum alloys contained large equiaxed ferrite crystals similar to those in Fig. Id. A portion of the % in. rod was hot rolled to 0.100 in., sandblasted, and cold rolled to 0.020 in. Strip tensile specimens having a 0.020x0.200 in. cross-section and a 2.25 in. gage length were machined from the sheet. The alloys containing molybdenum were subsequently annealed 1 hr at 1560°F. The iron strip was annealed 4 hr at 1300°F in wet hydrogen. The resultant structures are shown in Fig. 2a through h. The ASTM grain sizes were 1 to 3 as solution heat treated or 3 to 4 as annealed. The chemical analyses of the alloys are given in Table I. Carbon contents were obtained after the heat treatments in hydrogen. Alloy 15.9 pct Mo was tested as a cast alloy.'

Jan 1, 1956

By N. J. Grant, E. Gregory

The creep rupture properties of wrought aluminum powder products made from five grades of sintered aluminum powder were investigated at temperatures from 400° to 900°F for rupture times up to 1000 hr. The effect of stress concentrations on materials of this type was investigated by means of notched creep rupture tests. A tentative correlation was obtained between the creep rupture properties and the structure as revealed by electron micrographs. SEVERAL papers have been published recently concerning the production and properties of wrought aluminum powder products and their possible high temperature applications. Most of the published work in this field has come from abroad, notably Switzerland, and articles by Irmann and his colleagues were summarized in English recently.'.' Most of the papers published by Dr. Irmann are principally concerned with the retention of properties (by a product which is produced from extremely fine flake powder and is subsequently hot extruded) after heating to high temperature for prolonged times. The powder may be in atomized or flake form, and during hot working the applied pressure is reported to plastically deform the aluminum powder, thus breaking the oxide skin and welding the particles together. Irmann attributes the remarkable properties to the dispersion of oxide inclusions. Specifically, the product described by Irmann is one labeled SAP (Sintered Aluminum Powder) in which the initial flake powder is so fine that at least 50 pct of the flakes have one dimension of 2 microns or less. The composition of the starting aluminum shows in percent, Fe, 0.18; Si, 0.19; Zn, 0.06; Ti, 0.03; Cu, Mn, Mg, all nil; balance Al, approximately 99.5 pct. Aluminum is not the only material that has been found to have increased resistance to deformation at elevated temperatures when produced by powder metallurgy. It has been reported by Middleton, Pf eil, and Rhodes- hat platinum has a higher recrys-tallization temperature when produced by powder metallurgy and exhibits peculiar properties, many of which are similar to those of the aluminum powder products. Difficulties were encountered in explaining the reason for the strengthening in the case of platinum since the existence of the oxide is doubtful. The authors attributed the special properties to "a small amount of suitably dispersed porosity." This theory was supported by von -~eer-leder4 in the discussion to the paper, and the similarity between this method of hardening and that suggested by Rohner in his theory of age hardening was pointed out. R. de Fleury5 attempted to explain some of the properties in terms of the modulus of elasticity and elastic limit of alumina and aluminum while von Zeerleder examined the relationship between the yield strength and the reciprocal of the powder particle size. Boenisch and WiderholtQ dealt mainly with the corrosion resistance of the powder aluminum material and compared it with other aluminum alloys. The diffusion rates of other metals in SAP and pure aluminum have been compared by Seith and Lop-mann.' They showed that the alloying metals diffuse particularly quickly in SAP possibly due to the very fine grain size. The properties of the Alcoa products were given by Lyle.' The creep rupture properties of SAP and two of the Alcoa experimental powder products were compared by Gregory and Grant hnd it was shown that these products are vastly stronger at 900°F than are the best cast and wrought alloys at 600°F. Since the publication of these data, the authors have investigated two further aluminum powder products and it is the object of this paper to show how the high temperature creep rupture properties of the five materials vary with oxide content and with the structure as revealed by electron microscopy. Materials One of the five products, SAP, a sintered aluminum product, was supplied by the Societe Anonyme pourl Industrie de l,Aluminium, Neuhausen a/RHF, Switzerland, through Dr. R. Irmann, while the others, M276, M257, M293, and M255 were supplied by the Aluminum Company of America as experimental powder metallurgical products. M255- and M293 were made from coarse and fine atomized powders, respectively. The other materials were made from flake powders with significant differences in oxide content, the details of the type of powders used in the manufacture of these materials

Jan 1, 1955

By J. R. Bridge, D. A. Vaughan

The phase diagram of the Zr-H system over the range 0 to 65 atomic pet was determined by high temperature X-ray diffraction methods. Results show a eutectoid between a zirconium and the hydride phase. The eutectoid temperature was established at 560±10°C with a eutectoid composition of 42*3 atomic pet H. The hydride phase of the lowest hydrogen content is stable only above the eutectoid temperature, but is formed and retained in a metastable state during reaction of zirconium with hydrogen at temperatures below 560°C. One hydride phase is indicated that exists over the composition range 55 to 65 atomic pet H. RECENT increase in the industrial importance of zirconium has stimulated several investigations of the reaction of zirconium with hydrogen. Review of the literature on interpretation of absorption isotherms' ' shows that attempts were made to relate the observations to the room temperature hydride phases reported by Hagg.3 However, more recently Schwartz and Mallett' reported the existence of a new hydride phase, isomorphous with the lower hydride in the Hf-H system described by Sidhu.4 This phase was found adjacent to the metal in a diffusion gradient sample. In addition to the new phase, Schwartz and Mallett reported on only two of the five hydrides found by Hagg. Gulbransen" confirmed the existence of only three hydrides of

Jan 1, 1957

By W. Chubb

FOR the past several years there has been considerable interest in the development of zirconium and zirconium alloys for application in nuclear reactors. In a portion of the development work being conducted, attention has been given to the development of high-strength zirconium alloys. One of the most outstanding alloys developed in the course of this work is Zr-4 wt pct Sn-1.6 wt pct Mo.' Fabrication and Test Methods Over 50 ingots of zirconium containing either tin and molybdenum or both have been evaluated in the process of selection of an optimum composition. Most of these were prepared as 20-g are-melted buttons; a few were prepared by induction melting. All ingots were prepared by the me of Foote Mineral

Jan 1, 1958

By W. C. Hagel, H. J. Beattie

Variations in the secondary phase reactions of six nickel-and cobalt-base alloys were determined as a function of solu-tioning from 1700" to 2200°F and aging at 1200" to 1800° F for times up to 1000 hr. Room-temperature impact energies and hardnesses were also measured. Precipitation hardening of these alloys results mainly from the grain-interior formation of ? '; M23C6 appears principally as grazn-boundary cells which can be eliminated by intermediate high-temperature aging treatments. Cellular precipitation of ?' occurs up to 1500°F in cobalt-nickel alloys devoid of chromium, where precipitation by this mode can be attributed to a large degree of lattice disvegistery. THE usefulness of nickel- and cobalt-base alloys is dependent on balancing the strength and ductility provided by the solid-solution matrix, dislocation-type subboundaries, grain-boundary phases and genera1 precipitation within individual grains. Since equilibrium relationships for complex austenitic alloys are not easily fixed, a satisfactory balance

Jan 1, 1960

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor's analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By D. D. Button, L. D. Jaffee

INTEREST in the use of graphite as a high-temperature engineering structural material has recently increased markedly. However, actual use of this material has been limited, in part because information about its high-temperature mechanical properties has been lacking. The information needed includes not only reliable values for the properties, but also how to control these properties. Malmstrom, Keen, and Greenl have reported on the tensile and creep properties of some graphites above 2700° F (1500°C). They observed measurable creep under tensile loading at 4000 OF (2200 °C) and higher, with elongations of about 7 pct at 4500°F. Their typical elongation-vs-time curve showed the normal three stages of creep found for many metals at elevated temperatures. The specimens used were heated by passing an electric current through them. This method of heating caused a significant difference between the surface and axis temperatures, and may have affected the results. More recent work by kattus, in which the specfinens were also heated by their own resistance, showed very little plastic deformation for either slow or fast tensile testing or for creep testing. Work at this Laboratory, already reported,3 showed that for temperatures above 4500 "F and under conditions of slow tensile loading some commercial graphites exhibited elongations up to 20 pct. The work reported here is the continuation of a study of the tensile creep behavior of some commercially available synthetic graphites at temperatures up to 5300°F, and is preliminary to a more systematic investigation of the variables governing the high-temperature mechanical properties of graphite. MATERIALS TESTED The tests were conducted on six blocks from four lots of synthetic graphite bearing four different commercial-grade designations. These blocks were selected because their tensile stress—strain properties had been determined in previous work.3 Table I pre- sents the available information, supplied by the producers, on the processing of these materials. Also included in this Table are the densities and the tensile strengths at room temperature and 4500°F determined by the authors. EXPERIMENTAL TECHNIQUE The furnace used to heat the specimens for testing is shown in Fig. 1. The heating element was a graphite tube, 3-in. OD by 2 1/2 in. ID by 24 in. length. A spiral was cut into the 6-in. center portion of this tube to provide a high-resistance sec-

Jan 1, 1961

By J. W. Pugh, Sam Leber

Single crystals of tungsten were made and deformed in tension at 3000°C. The slip traces so formed on these crystals were analysed to determine the apparent slip system. Results indicate that deformation occurs in the<III> direction on planes of maximum shear stress. This determination agrees with the early work of Taylor and Elam on other body-centered cubic crystals at lout temperatures. SLIP in face-centered cubic and hexagonal close-packed metals has consistently manifested itself in straight traces which indicate that glide takes place on planes of highest atomic density and in directions of closest packing. The slip traces observed on body-centered cubic metals are, on the other hand, frequently branched and wavy, and indicate that while glide takes place in the direction of closest packing, it does not necessarily choose the plane of highest density. The early work of Taylor and Elam1 4 indicated that glide took place in the close-packed direction on planes close to those defined by the maximum shear stress. Subsequent investigations have tried to rationalize these observations in terms of an elementary process on the close-packed planes (110). For example, Elam5 and Grenin~er&apos; have suggested alternate glide on nonparallel (110) planes with the observed result that the summation of these glides results in a trace which defines some plane other than{110). Madden and chen7 have recently reviewed the phenomenological and theoretical aspects of noncrystallographic slip. More recently Koehler&apos; has presented a model of dislocation propagation which permits another rationalization. He indicated that dislocation loops are transferred from one glide plane to another by double cross-slip of screw segments. It is reasonable to assume that, on the average, such transfers may result in a trace which approaches the plane of maximum shear stress. The work described in this paper will show that

Jan 1, 1961

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;&apos;-&apos; these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-&apos; and ductility,&apos; and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.&apos;-&apos; Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963