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By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

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

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known&apos; that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By R. H. Hiltz, R. W. Douglass

Large-grain specimens of iodide titanium prepared metal-lographically were stain etched using the technique of New York University as modified by Watertown Arsenal Laboratories. Orientations of grains showing an abnormal response to stain etching were determined by back-reflection X-ray techniques. X-ray results showed that a-titanium grains, oriented such that their basal planes were parallel to the polished surface, have a slower reactivity to stain etching than any other orientation. Grains oriented such that their basal planes made small angles with the polished surface exhibited reaction rates between that of the true basal orientation and the normal rate. As the angle with the surface increases the reactivity increases up to a maximum angle of 14 deg. Basal planes making an angle with the surface of greater than 14 deg show normal reactivity to stain etching. These data, plus work on polycrystalline specimens, indicate that the oxidation rate of titanium might be reduced by correct alignment of crystal planes. ThE earliest observed phenomenon in the micrography of titanium was the occurrence of a grains which exhibited no birefringency. Even though a titanium possesses a hexagonal-close-packed structure and should be optically anisotropic, it can appear optically isotropic, when the crystal is so oriented that its intersection with the polished surface is perpendicular to the axis of symmetry. During the develoment of color staining techniques for titanium: it was noted that the a phase did not stain uniformly. Staining of specimens of commercially pure titanium resulted in a micro-structure of blue-colored grains, among which were randomly oriented a few grains exhibiting colors between the initial yellow and the final blue color. Under polarized light, these off-colored grains appeared to be optically isotropic. More intense study with polarized light, however, showed only the yellow grains to be isotropic. The intermediate colored grains exhibited weak birefringency, which at first glance is not detectable due to the strong birefringency of the surrounding structure. Aminoff2 and Straumanis3 have previously shown that in zinc the basal orientation is less reactive than other orientations. Leidheiser4 showed the same thing to be true for the hexagonal-close -packed configuration of cobalt. Thus, it would appear that the basal-plane orientation is responsible for the abnormality in stained titanium. Later work by Leidheiser5 on cobalt has shown that other planes besides the basal plane exhibited reaction rates slower than the normal rate. Reported planes were the (100), the (1011) and several planes making small angles with the basal plane. The last observance appears not to be due to the reactivity of the reported plane but due to the reactivity of the basal plane which is very close to being parallel to the surface. There are, then, two possible explanations for the range of colors observed in stain-etched a titanium. Since extensive research on the effect of orientation on surface reaction has failed to provide any definite trend, these two explanations are not adequate in themselves. Planes showing the retarded reactivity differ not only for different crystal structures but for metals of the same crystal structure and even for different reactions of the same metal. Tragert,6 Leidheiser,7 Tammann,6 and wagner9 have shown copper to exhibit retarded reactivity on the (111) plane. However, Leidheiser10 has shown that under other conditions the retarded reactivity of copper is associated with the (100)

Jan 1, 1960

By T. N. Rhodin

There can be two types of films on solids, those which are stable in mono-layers and those which tend to aggregate into three dimensional structures. A great number of metal films formed by condensation onto a solid base are unstable in the sense that they will aggregate into crystals providing the atoms possess sufficient surface mobility. The crystalline structure of the film is strongly influenced by the base in many systems and, in some cases, a single orientation prevails when the force fields around the atoms in the supporting crystal are sufficiently strong.&apos; Relatively little is available in the literature about the nature of these forces and the role they play in promoting a preferred orientation of the atoms arriving at the substrate surface. An understanding of their periodicity and magnitude relative to the surface forces characteristic of the film itself should provide insight into the critical dependence of film orientation on the nature and temperature of the substrate. In addition, this effect may be very useful in preparing samples for surface studies. The study of the physical and chemical characteristics of pure metal surfaces has been severely handicapped by the presence of strongly adherent foreign films. Furthermore, the randomness of the surface orientation has obscured interpretation of experimental results. Evaporation of metals in high vacuum onto carefully selected substrates under ideal conditions for preferred orientation appears suited to the preparation of flat, oxide-free, oriented films for surface reaction studies. Many factors influence their structure and some understanding of the mechanism of their formation is a necessary prerequisite for obtaining satisfactory surfaces for study. The dominant factors in defining film structure are film thickness and growth rate and the nature, condition, and temperature of the substrate. GENERAL ASSEMBLY The system was enclosed in an 18 in. bell jar which rested on an L-shaped neoprene gasket on a ground steel plate as indicated in Fig 1. Rapid evacuation of the system to 10-6 mm mercury was facilitated by a 4 in. manifold, 2 in. packless valve, and an extra large diffusion pump. Suitable arrangement of valves on a secondary manifold readily permitted introduction of purified gases

Jan 1, 1950

By E. J. Whittenberger, F. N. Rhines

The formation of casting porosity is viewed as a nucleation and growth process with solidification shrinkage and gas precipitation as cooperative driving forces. Experimental evidence evaluating the individual contribution of each force confirms the major premise that microporosity is nucleated by gas precipitation. Additional data disclose the effects of the identity and quantity of gas, the temperature range of freezing, and the freezing rate upon the amount and distribution of porosity in light metal castings. POROSITY, as it commonly occurs in metal castings, has been ascribed to the contraction that accompanies the freezing of the metal, to the evolution of dissolved gases from the liquid during cooling and freezing, and, most frequently, to a combination of the two.&apos;" "Pipe" formation is universally associated with solidification shrinkage; spherical "gas holes" are understood to be retained bubbles of gas; but the origin of microporosity, which usually exhibits an irregular or scalloped outline when viewed in cross-section, remains a subject of continuing debate.", &apos; The present research constitutes an endeavor to show what parts are played respectively by shrinkage and gas evolution in the initiation and growth of micropores and what factors determine their number, size, shape, and distribution. A preliminary outline of the mechanism of cavity formation in castings will serve to coordinate the experimental findings that will be reported and will at the same time provide a general theory of the origin of casting porosity. Basic to the mechanism of cavity formation that will be proposed are the following established facts: 1—that liquid metals and alloys contract gradually during cooling down to the freezing range, where a relatively large contraction, known as the "solidification shrinkage," takes place (exceptions in bismuth and gallium being noted);&apos; 2—that the capacity of liquid metals and alloys for dissolving gases diminishes with cooling until, in the freezing interval, a large decrease takes place (various exceptions being noted and excluded from present consideration) ;.: and 3—that freezing proceeds counter to the direction of heat flow, the freezing front most commonly being composed of a system of tapering dendrite stalks and side arms which are coarser the lower the freezing rate and which protrude into the liquid for a distance that is greater the longer the freezing temperature interval of the alloy and the smaller the thermal gradient.&apos; The mechanism by which voids are generated

Jan 1, 1953

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-&apos; to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6&apos;9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3&apos;5&apos;7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5&apos;7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f &apos;([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1&apos; Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-&apos; of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen&apos; -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports&apos;92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established&apos;-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. &apos;This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By Nicholas J. Grant, Noboru Komatsu

Electron-micrographic studies and hardness tests were made of an internally oxidized dispersion-strengthened Cu-12 vol pct SiO2 alloy follozuing longtime annealing at elevated temperatures. The rate of coarsening of SiO2 particles and the relationship between hardness and interpavticle spacing were Dispersion -strengthened alloys exhibit a remarkable stability of structure and properties at elevated temperatures compared with conventional alloys; nevertheless, when they are exposed to high measured. The rate of coarsening of SiO2 particles is controlled by the decomposition of SiO, rather than by the diffusion rates of silicon or oxygen through the copper matrix. The mechanism of coarsening was also studied by using a diffusion-couple technique. temperatures, weakening takes place as a result of coarsening of the dispersed phase. The theoretical treatment of the coarsening of dispersed phases has been treated by Greenwood,1 wagner,, and others3 by considering the interfacial energy of dispersions and the diffusion of solute atoms. Recently, experimental work on the coarsening of relatively insoluble, finely dispersed cobalt particles in copper was reported by Livingston,4 and on aluminum oxide in nickel by Dromsky, Lenel, and Ansell;5 according to these investigations, the rate

Jan 1, 1964

By Harry C. Gatos, Frank J. Bachner, Mario D. Banus

The portion of the Nb-Sn phase diagram between 75 and 79 at. pct Nb at temperatures near the liquidus has been investigated by melting alloys of known composition and examining the microstmc-tzlres resulting when these melts were quenched. The Nb-Sn samples were contained in magnesia sleeves, and were mounted in a high-pressure apparatus. It was shown that Nb3Sn me1ts by a peri-tectic decomposition and that the composition of the compound Nb3Sn at the peritectic horizontal lies between 77 and 78 at. pct Nb. Analysis of the phases present in the samples was accomplished by anodic staining techniques and an electron-microbeam analyzer. DURING the past several years a great deal of work has been devoted to the Nb-Sn system, and the bulk of this work has been primarily concerned with the intermetallic phase Nb3Sn. However, the melting characteristics of Nb3Sn have not been investigated because of the difficulty in maintaining known compositions due to tin losses by vaporization, and the added difficulty of containing Nb-Sn alloys without sample-container reaction at the high temperatures involved. This paper reports on the development of a technique for containing Nb-Sn alloys under pressure high enough to prevent tin losses at temperatures in excess of the liquidus. Using this technique, melts of known composition were made and a phase diagram near the liquidus is proposed based on the microstructures resulting when these melts were quenched. EXPERIMENTAL The Nb-Sn alloys weighing 0.7 g each were prepared in the form of cylinders. Niobium powder, -200, +325 mesh, and tin shavings with a minute amount of tin powder for a binder were mixed in the desired proportions and cold-pressed at 50,000 psi in a 0.150-in. die. This cylinder was then enclosed as shown in Fig. 1, and the entire arrangement mounted in a 2.6-in. pyrophyllite tetrahedron.&apos; The desired temperatures (-2500°C) presented several problems in high-pressure container materials. Boron nitride, the usual sample holder, was found to react with niobium to form the nitride. However, MgO cans and plugs machined from refractory rods did not melt nor react with the sample. Thick tantalum contact disks were used to carry the large currents (~450 amps) to the graphite heater, since tantalum did not melt and had enough strength to prevent extrusion of the sample. It was further observed that the graphite heater and tantalum disks could not be in direct contact with the pyrophyllite because it melts and decomposes at these temperatures to kyanite and coesite (SiO2),2 the former reacting with graphite and the latter with tantalum to form the silicide. The use of a MgO outer sleeve

Jan 1, 1965

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all&apos; and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all&apos; and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.&apos;-&apos; Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.&apos; These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum&apos; and later by Long et al.&apos; produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.&apos; The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan&apos; has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.&apos; As a check

Jan 1, 1957

By R. I. Jaffee, C. T. Sims, C. M. Craighead

The fabrication of rhenium metal by powder metallurgy techniques is discussed. The following physical and mechanical properties have been measured and are reported: lattice constants, melting point, electrical resistivity, thermal expansion, spectral emissivity, modulus of elasticity, tensile properties and ductility at room and elevated temperatures, work hardening, recrystallization, grain growth, and oxidation resistance. IT is only occasionally that a metal reaches present-day technology with as little known about its properties as element No. 75, rhenium. Relatively scarce to date, it has been studied only infrequently and used less. Previous work on rhenium has been carried out primarily by European scientists. However, realization that rhenium occurs in commercial quantities in the United States recently has focused attention on this metal. Rhenium is a very dense high melting hexagonal-close-packed metal. Like tungsten and molybdenum, its highest oxide is volatile. However, when protected by reducing or inert atmospheres, its strength at high temperatures is greater than that of tungsten. Rhenium work hardens more than any other known pure metal, but, on annealing, becomes quite soft and ductile. Its vapor pressure is approximately that of tantalum, but it does not enter into the so-called "water cycle" nearly as readily as does tungsten. (The water cycle is a deleterious phenomenon causing blackening of lamp bulbs and vacuum tubes with subsequent failure of the filaments.) These and other properties, some already known and some found as a result of the current researches, have indicated that rhenium has many potential uses, primarily of an electrical or electronic nature. Rhenium or its alloys soon may be found in service as electron-tube filaments, cathodic emitters, or as electrical contact materials. In addition, rhenium or its alloys have potential use in such devices as high temperature thermocouples, and high wear-resistant parts such as precision instrument points. Rhenium, in the form of potassium perrhenate, was made available for this study by the Kennecott Copper Corp. The potassium perrhenate was reduced to rhenium metal in two stages, accompanied by leaching to remove potassium in the form of hydroxide. This impure metal was then oxidized to rhenium heptoxide and dissolved in water. The solution was neutralized with ammonium hydroxide to produce highly purified ammonium perrhenate, a typical analysis of which is shown in Table I. The ammonium perrhenate was ground to —325 mesh in a rubber-lined ball mill with Burundum balls. This operation caused a certain amount of impurity pickup, as reflected in the rhenium analysis shown in Table I. The fine ammonium perrhenate was reduced to metal with hydrogen. Particle size of the powder ranged from 1 to 25 microns, as illustrated by Fig. 1.

Jan 1, 1956

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;&apos; it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.&apos; Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander&apos; and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By Henry R. Piehler

Continuous seven- and nine teen -filament close-packed silver-steel filamentary composites mere tested in tension. For purposes of comparison, the tensile behavior of the composite was predicted from the measured properties of the individual com-ponents. It was assumed that the axial strain is the same in both components and that the contribution of each component to the composite flow stress is proportional to its volume fraction. Good agreetnent was obtained between the observed and predicted tensile behavior. However, the composite elongation at fracture was about twice that observed when the individual steel wires were tested alone. Composites in which the filaments were widely spaced failed by the consecutive fracture of the filaments. In composites with closely spaced filaments, a composite instability preceded frachcre. These effects are explained in terms of a lateral restraint to the necking of the filaments which develops in the deforming composite. TWO-COMPONENT or composite materials are increasingly being developed and used as structural materials. Of all the composite geometries used, the filamentary configuration has proved to be the most successful. Polymer-bonded fiber-glas, the most common of the filamentary composites, has been investigated most extensively to date. One explanation of the behavior of fiberglas1 suggests that the load transfer between the glass fibers and the polymer matrix occurs primarily through friction. Bond separation between the fibers and the matrix is presumed to occur at very low stresses. Subsequently, only frictional bonding can provide for the transfer of load from the matrix to the fibers. The force normal to the fiber-matrix interface which gives rise to this friction is assumed to arise from the matrix shrinkage which occurs during solidification. The behavior of metallic filamentary-composite materials would be expected to differ from that of fiberglas in several significant aspects. Residual stresses resulting from differences in thermal contraction can be kept to a minimum by proper heat treatment. A strong wetted bond is formed between the two phases. In brazed joints,2 for example, the interphase bond is sufficiently strong that the weaker material will fail before separation occurs at the interface. Most metal filaments can undergo appreciable amounts of plastic deformation before failure. Failure by plastic instability or necking frequently occurs in metallic filaments, but not in glass fibers tested at room temperature. Differences between the behavior of fiberglas-polymer and metallic filamentary composites have indeed been observed in composites containing various types of metallic filaments in a silver matrix.3,4 At strains of the order of 10-2 pct, all the deformation was accommodated by the silver matrix. Hence, the strength of the composite depended only on the fiber concentration and not on the nature of the fiber. At higher strains, the strength of the composite increased when filaments with higher work-hardening rates were used. Surface slip line observations on a silver-mild steel composite that had been stretched 4 pct showed that an appreciable amount of deformation occurred in the filaments. Work on tungsten-copper filamentary composites5 has shown that the ultimate tensile strength for varying filament fractions followed a linear mixture rule. Assuming that the axial strains in both filaments and the matrix are equal, this linear mixture rule can be expressed as: The subscripts c, f, and m refer to the composite, filaments, and matrix, respectively. A and V are the area and volume fractions of each component. sc and of are the ultimate tensile strengths of the composite and the filaments. sm is the flow stress of matrix at a strain equal to the elongation at failure of the filaments. However, the tungsten filaments can undergo only a limited elongation before they fracture without an appreciable reduction in area. A composite containing more ductile filaments might indeed deviate from this linear mixture rule for the ultimate tensile strength, since filament failure by necking might be arrested by the matrix. SPECIMEN PREPARATION Specimens were prepared from 0.8 pct carbon steel piano wires of 0.015 in. initial diameter. The wires were given a thin nickel flash and a silver plate varying in thickness from 0.015 to 0.007 in., depending on the filament fraction desired. In order

Jan 1, 1965