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By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By W. H. Herrnstein, J. B. Clark, E. C. Utley, A. J. McEvily

The ratio of the endurance limit (10' cycles) to tensile strength of age-hardened aluminum alloys is approximately 0.3, whereas the ratio for annealed alloys is about 0.5. The lower value for the age-hardened alloys has been associated with the instability of coherent precipitate during cyclic loading, but it has not been definitely established whether this instability is due to overaging or reversion during cyclic loading. The results of the present investigatzon support the reversion viewpoint. In this work specimem of 2024-T4 aluminum alloy were aged for 16 hr at 150°C after cycling for 10 pct of the life at 25.000 psi. These specimens were then tested to failure and exhibzted a marked increase in fatigue life. It is proposed that during the early stages of fatigue in this alloy dislocations cut through the coherent precipitate and bring about the reversion of the precipitate. Subsequent aging at 150ºC induces reprecipitation in the precipitate-free zones so that the weakened regions are strengthened and the fatigue life is extended. It Is recognized that the fatigue strengths of precipitation hardened aluminum alloys are unusually low relative to their tensile strength.'-= This feature is illustrated in Fig. 1 where it can be seen that age-hardened alloys have lower fatigue ratios (the ratio of the fatigue strength to the tensile strength) than those in the annealed or cold worked state. Further, as shown in Fig. 2, the more an alloy is dependent upon precipitation hardening for its total strength, the lower is the ratio of the fatigue strength to the tensile strength. This state of affairs has been associated with an instability of the metastable metallurgical structure of precipitation hardened aluminum alloys during cyclic loading. Evidence2 in support of this view is that the fatigue ratio increases in these alloys as the test temperature is lowered, thereby indicating that thermo-mechanical instability, rather than some other factor such as a non-uniform distribution of precipitate, is the factor responsible for the low fatigue ratio at room temperature. Two mutually exclusive proposals have been ad- vanced to account for this instability. Hanstock has proposed that overaging takes place during cyclic loading, and in support of this view, Broom et a1.2 have indicated that an overaging process might be promoted by the large numbers of vacancies which are created during cyclic loading. The creation of vacancies by radiation4 has been shown to lead to rapid overaging. Hanstockl obtained visual evidence of overaging in an aluminum alloy after cyclic loading, but in this instance it has been pointed ou? that because of the high frequency used (60,000 cpm) the observed effect may have been due to normal high temperature precipitation around energy dissipating cracks. Efforts to discern visual evidence of overaging in this alloy at lower test frequencies were not successful.3 The alternative postulate3 is that reversion takes place during cyclic loading and leads to localized soft spots at which fatigue cracks are readily initiated. Evidence for this process has recently been provided by Polmear and Bainbridge5 who demonstrated metallographically that regions depleted of precipitate were created during cyclic loading of an aluminum alloy. Inasmuch as precipitate particles bordering the depleted region had not grown in size, it was concluded that the solute atoms which had constituted the missing particles had gone back into solution. No mechanism for the reversion process was presented. The present study was undertaken to investigate further the conditions leading to instability during cyclic loading, and to determine whether reversion or overaging had taken place as a result of cyclic loading. BACKGROUND AND TEST PROCEDURE In order to differentiate between the processes of reversion and overaging, rest periods at an elevated temperature, which ordinarily would insure additional precipitation, were used in this investigation. It was expected that after a period of cyclic loading an elevated temperature rest period would result in a decrease in the remaining life of the specimen if overaging were occurring during cyclic loading, whereas in the case of reversion, reprecipitation would occur and the fatigue life would be extended. Such an expectation is based on the assumption that the crack-nucleation phase is a significant portion of the total fatigue life, and that such a treatment is of influence in the crack-nucleation stage and is relatively unimportant thereafter.

Jan 1, 1963

By R. E. Cech

Particles -3 to 30 µ diam of a 29.5 pet Ni, 70.5 pet Fe alloy after being melted and solidified while falling through a hydrogen atmosphere were found to contain a distortion-free body-centered-cubic phase. In most particles, the amount of body-centered-cubic phase approaches or equals 100 pet. It was shown by a series of experiments that this phase forms directly from the liquid. It is pointed out that a mechanism previously suggested in recent papers on the theory of the liquid-solid transformation can account for the solidification of body-centered-cubic phase in a temperature range where face-centered-cubic is the stable phase. IN the course of an operation to produce powders for a study of the martensitic transformation in Fe-Ni alloys, an unexpected phenomenon was observed. Powders of a 29.5 pet Ni alloy, which has a subzero M, temperature, were found to contain considerable amounts of a body-centered-cubic phase at room temperature. The experiments to be described were designed to elucidate the mode of formation of this unexpected phase. Experiments and Discussion An alloy containing 29.5 wt pet Ni, balance iron, was vacuum melted from high purity electrolytic iron and carbonyl nickel shot and solidified in the crucible. The metal was converted to oxide, ground to 100 pet <37µ, pressed to a cake, and homogenized 20 hr at 1350°C. To insure homogeneity the grinding, pressing, and homogenizing heat treatment was repeated a second time. The oxide was then ground to 100 pct <37µ and hydrogen reduced at 500°C. The reduced powder was given a spheroidizing treatment to produce spherical cast particles. The treatment consisted of dispersing the particles in hydrogen and allowing them to drop through a vertical hydrogen furnace set to a temperature higher than the liquidus of the alloy. This operation, commonly known as shotting, has been described more fully elsewhere.&apos; The powder produced by this method was found to contain approximately equal parts of body-centered-cubic and face-centered-cubic phases. A magnetic separation technique, previously described,&apos; was applied, and it was found that particles were either completely face-centered-cubic or nearly completely body-centered-cubic. The microstruc-

Jan 1, 1957

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.&apos;-&apos; This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,&apos; by the copper-decoration technique,&apos; by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18&apos;19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By Don M. Jackson, Robert W. Howard

Techniques for the epilaxial growth of single -crystal silicon carbide films on silicon were developed. The vapor-phase decomposition and bydrogen reduction of silicon tetrachloride (SiC14) and Propane (C3H8) resulted in clear films of silicon carbide, lip to seveval microns in thickness. The growth took place in a horizontal . silicon epilaxial reactor at 1100°C (pyrometer) at a rate of- 3000Å per minute. Electron diffraction and X-ray diffraction studies demonstrated that the films were single-cyrstal, ß -phase, or cubic silicon carbide. SiO2 film were used to mask areas of the silicon sur-lace in order that the silicon carbide might be grown in controlled geometries. Both n- and p-type films were grown on p-type silicon waters.. Heavily doped silicon films of the same conductivity type as the silicon carbide films were deposited over the silicon carbide in order to affect better probe contact to the structures. when n-type silicon carbide mesas were grown on p-type silicon substrates the de vollage-current relationships between films and substrates were that of junction diodes. These diodes showed a sensitivity to while light ill that the incident light increased forward- and reverse-satro,ation currents, P-type silicon carbide mesas grown on p-type silicon were ohmic rather than rectifying in their voltage -current relationship. No conclusions could he reached concerning heterojunc-tiou rectification in the structure. SILICON carbide is a semiconductor with many interesting properties. It decomposes at temperatures above 2200°C.1 It occurs in two general crys-tallographic forms—hexagonal (a Sic) and cubic (ß Sic)—with the cubic form having a forbidden-gap energy of 2.32 ev and the hexagonal form (specifically the 6H polytype) a gap energy of 2.86 ev.3 It behaves as an extrinsic semiconductor at temperatures approaching 5003C. It has been shown to have a high resistance to radiation damage4 and p-n junctions formed in Sic have been shown to radiate visible light under forward- or reverse-bias conditions. Epitaxial silicon carbide on silicon carbide has been successfully grown through the use of a variety of techniques, such as gaseous cracking of SiCL4 and CC4, nearly all of which require a deposition temperature above 1500°C.6 This paper will cover very recent work on the gas-phase deposition of highly ordered films of silicon carbide on high-quality silicon single-crystal substrates. The films have been shown to ex- hibit junction-rectification properties when geometrically isolated regions are electrically biased with reference to the silicon substrate. There will be no discussion of the mechanism of heterojunction rectification, but the methods of film fabrication, geometry control, and structural evaluations will be covered in detail. Electron diffraction, X-ray diffraction, and diode electrical properties were used to characterize the films and the junctions. GAS-PHASE DEPOSITION OF Sic The techniques for the deposition of silicon carbide films were a logical outgrowth of the standard silicon epitaxial process. The major premise followed was that, for any film to nucleate in an ordered fashion where there is considerable mismatch in lattice parameters (in this case 22 pct), an extremely clean, damage-free substrate surface must be presented to the gas stream. Thus a standard gas-phase HCl etching step was used to prepare the substrates for growth. A minimum of 5 µ of substrate-surface material was removed prior to the deposition of Sic overgrowth films. The techniques used for growing silicon carbide films were those of growing silicon alone, with the added injection of a hydrocarbon gas into the hydrogen and silicon tetrachloride gas stream. The hydrocarbon gases used thus far have been research-grade (99.99 pct) methane (CH4) and propane (C3H8). Propane ultimately gave the best results. The gas flows were controlled through a panel shown schematically in Fig. 1. A hydrogen main stream of 30 liters per min passed through the horizontal quartz-tube epitaxial reactor, while SiC14, C3H8, HC1, and doping gases were injected as side streams. The

Jan 1, 1965

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.&apos; They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By B. A. Wilcox

ThERE are several reports in the literature which indicate that both solid-solution hydrogen and hydride precipitates can promote low-temperature em-brittlement of tantalum.1-3 For example, Imgram et al.2 showed that hydrogen additions in the range of 140 to 580 ppm promoted a ductile-to-brittle transition at slightly above room temperature in both wrought and recrystallized tantalum. This contrasts with the observation that tantalum of norma1 purity is very ductile, even at liquid-nitrogen temperature. Imgram et al. also found that hydrogen additions caused a deterioration of notch tensile properties of tantalum. The purpose of this communication is to present some limited evidence that hydrogen can also cause fatigue embrittlement of tantalum. The material used in this investigation was wrought, stress-relieved (1000°C, 1 hr), are-melted tantalum rod (5/8-in. diameter) containing the following impurities in weight percent: 0.005 C, 0.007 02, 0.0005 H2, 0.003 N2, 0.08 Cb, 0.01 W, and 0.01 Fe. Hydrogen charging was done in an atmosphere of flowing dry hydrogen for 3 hr at 600°C, followed by an homogenizing anneal in purified argon for 15 min at 600°C, and cooling in an argon atmosphere. Typical micro-structures of the hydrogen-free and the hydrogen-charged materials are shown in Fig. 1(a) and Fig. 1(b), respectively. Fig. 1(b) shows the appearance of hydride precipitates which, in many cases, formed preferentially parallel to the rod axis. The hydride dispersion was uniform across the diameter of the specimen. The fact that the precipitate was a tantalum hydride was tentatively confirmed by X-ray diffraction on a metallographically prepared surface. After hydrogen charging, chemical analyses by vacuum fusion revealed the hydrogen content to be 0.0295 wt pct. In addition, the oxygen and nitrogen contents were slightly raised to 0.0095 O2 and 0.005 N2.

Jan 1, 1964

By W. A. Backofen, M. L. Ebner

SINCE the early work of Gough with Hanson and Wright,l-3 the study of fatigue has been characterized by experiments on single crystals only in recent times.9-10 Now, increasing attention is given to this aspect of fatigue research for the insight that it may provide into details of mechanism. The investigations have concentrated to a large extent on the development of deformation markings on fatigued crystals, and have shown the cracks to originate in slip bands possibly preceded or accompanied by slip-band extrusions. Experiments of special interest to the present work were conducted by paterson5 on copper crystals and involved both metallographic examination and measurement of change in flow stress. Crystals were cycled in alternating tens ion-compress ion with a constant plastic shear-strain amplitude of approximately 0.8 pct, and were particularly revealing for their demonstration of hardening with accumulated strain similar to that in unidirectional straining, through an easy-glide stage I followed by a stage II of rapid hardening; deformation was not continued beyond 40 cycles, however, so that the eventual course of the hardening curve could not be decided. For the conditions used by Paterson, surface slip markings were similar to those observed in unidirectional straining, but there were no X-ray asterisms and no deformation bands on the surface. In current thinking about the nature of fracture in fatigue, two views relative to mechanism are generally acknowledged, with the reservation that both could apply simultaneously in some measure. As one possibility, fracturing across a slip plane is regarded as a result of loss of cohesion from the creation of many point defects by dislocation movement under the cyclic loading.&apos;&apos; On the other hand, fracture has also been taken to follow as a consequence only of the geometry of slip at a free surface, consisting of offsets and crevices which eventually become fatigue cracks.12, l3 The work of McCammon and Rosenbergl4 showing fatigue in polycrystals at 4.2oK makes clear that any long-range diffusion of point defects is unnecessary, yet studies such as those of Forsyth and stubington15 show that accelerated diffusion may be a characteristic of deformation under fatigue loading. Interest in obtaining data of possible use for resolving such questions led to the experiments described below. Copper crystals were conveniently loaded in alternating four-point bending at constant deflection, a test condition shown to approximate a constant plastic strain amplitude for a wide range of axial orientations. The method of testing was not readily adapted to extensive study of temperature effects, but an investigation of the geometry of crack formation could simply be made by orienting,the slip direction at different angles to the surface. EXPERIMENTAL PROCEDURES Single crystals were grown by a modified Bridgman method in a stationary gradient furnace under an atmosphere of purified dry nitrogen. Purity of as-grown crystals was 99.999 pct as determined by spectrographic analysis plus vacuum fusion and gravimetric analyses for oxygen and sulfur, respectively. Crystals were of reasonable perfection as evidenced by a critical resolved shear stress at 10 deg from (110) of 60 g per sq mm and half-width of a (400) X-ray diffraction line from one crystal of

Jan 1, 1960

By K. L. Moazed, G. M. Pound

An investigation was made of the deposition of silver from a thermal beam onto tungsten field-emitter tips at 300°K. "Island"-type nuclei were observed to form and grow. The nucleation of silver crystals occurs preferentially on non-close -packed planes of a tungsten tip at a critical volume free-energy change of about —2900 cal per cc. The adatom population which is critical for appreciable nucleation rate of silver crystals is about 0.2 of a monolayer and is essentially independent of beam flux, time, and source temperature. This result is strong evidence that a metastable equilibrium exists between adatoms and critical nuclei, as assumed in the present theory. SOME of the more significant studies of nucleation in deposition of metals from vapor beams have been conducted by measuring the thermal beam flux which is critical for appreciable rate of nucleation on a substrate surface held at a given temperature.&apos;2 The observed critical supersaturations may be described in terms of Eq. [7] which was derived3&apos;3a on the model of an adsorption, surface migration, and statistical fluctuation mechanism. However there usually made with a low-power optical microscope, a fairly insensitive method of detection. The object of the present study was to overcome some of these difficulties by measuring the critical supersaturation for condensation of a thermal beam of silver onto a tungsten field-emitter tip. Such a tip may be cleaned by electrically heating it to a high temperature in situ, and the high vacuum obtainable in a field-emission tube (10-10 torr) precludes adsorption of residual gases for convenient periods of time. Furthermore, the degree of cleanliness, the orientation, and the state of imperfection of the tip may be ascertained from the field-emission pattern. Detailed explanations of theoretical considerations and experimental procedures relating to the field-emission microscope may be found in a number of excellent review articles12&apos;13 and thus only a brief description will be given here. The electronic work function of a metal is defined as the energy that an electron needs to escape from the potential field of the solid. By applying a large field between the surface of the solid and a suitable collector, it is possible to free the electrons by the tunnel effect. Fields of approximately 30 million v per cm are needed to produce this effect, and such fields are obtained in practice by using microscopic surfaces of high curvature (tips). Because the work function of a metal is a function of surface orientation, the emission from the various planes is different, and thus it is possible to obtain a representation of the surface in the emission microscope. In general, the work function is higher for the more densely packed planes. Fig. 1 shows a pattern for "clean" tungsten in which the central dark region represents the (110)

Jan 1, 1964

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.&apos; Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found&apos; that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954

By R. Webeler

In order to study the role of work hardening in the fatigue process, use was made of the great sensitivty of the resistivity of AuCu to cold work. A change of the resistivity of AuCu of the order of 1 to 2 pct at the temperature of liquid nitrogen was found to occur as a consequence of severe fatigue. ACCORDING to Orowan&apos;s theory,&apos; the process of fatigue In metals 1s associated with the production of a number of small regions which have undergone strain hardening. This phenomenon is supposed to occilr even if the stress applied during fatiguing is always smaller than the yield stress. In an attempt to verity the existence of such regions, Welber and Webeler&apos; undertook to detect the stored energy associated with severe fatigue in copper. Previous experiments" had shown that the energy stored in a sample of copper which has been cold worked by torsion is released in the temperature range between 150" and 250°C when the sample is heated from room temperature and that no more energy is released (or absorbed) between 250" and 450°C. In particular the stored energy amounted to 0.41 cal per g for a case in which the mechanical energy expended in twisting the sample was 11.9 cal per g. In the case of fatigued copper, however, no release of stored energy could be detected between 150" and 250°C, so that the experimental error of &0.02 cal per g represents an upper limit for the amount of energy stored in strain hardening., It seemed desirable to attack the problem in a new fashion. For this purpose, it was decided to make use of the fact that, if an alloy capable of undergoing the order-disorder transition is ordered and then cold worked, the resistivity, p, increases very greatly above the value for the ordered state even if the deformation is very small. Some insight into the nature of the fatigue process may be obtained then by measuring the resistivity of an ordered sample before and after subjecting it to fatigue. For reasons which will become apparent from the following remarks, considerably more can be learned by carrying out the resistivity measurements at two different temperatures. In the case of a material containing impurities, vacancies, dislocations, or other imperfections of essentially atomic dimensions, the resistivity, p, according to Matthiessen&apos;s rule, can be represented as a sum of two terms p = p, + p, where p, is the (temperature dependent) resistivity of the pure metal, and p, is the temperature independent contribution of the imperfections. Briefly, the physical basis for this rule is the following: The main contribution of the impurities in question to the resistivity results from the fact that they interrupt the periodicity of the lattice and thus scatter the conduction electrons with a probability which is almost independent of temperature. In order that this be the case, it is necessary that the&apos; extension of the impurities be small enough—roughly less than one electron mean free path—so that their main effect on the resistivity occurs for the foregoing reason. If an alloy like AuCu is partly or completely disordered by quenching from an appropriate temperature, Matthiessen&apos;s rule also applies to a very good approximation* with p, representing in this case the resistivity po of the ordered sample and p, the additional (temperature independent) resistivity due to the disorder. In general, the disorder can be represented in terms of atoms which are displaced from their "proper" positions in the superlattice and which thus qualitatively represent the imperfections in the superlattice responsible for the term p,. Since the misplaced atoms are distributed at random throughout the super-lattice, their contribution to the resistivity still can be considered in terms of the scattering of conduction electrons by lattice defects. The situation is somewhat more complex in the case of an alloy disordered by cold work because the process of disordering here does not involve a random redistribution of the atoms; however, Matthiessen&apos;s rule also holds in this case. Whenever Matthiessen&apos;s rule does apply, the values of the quantity /3 = (p? — /(T, — T,), where p, and p, are the values of the resistivity at two fixed temperatures, T, and T,, respectively, is constant (independent of p,) for a given alloy or metal. In particular, if a sample of AuCu is subjected to ordinary cold work, the value of /3 remains equal to Po, the value for the ordered material. According to Orowan&apos;s theory,&apos; as remarked before, a fatigued sample contains a large number of isolated severely cold-worked regions, which make up only a small proportion of the metal. Thus, if a sample of AuCu initially in the ordered state is fatigued, more or less disordered regions will be produced within the ordered material. If these regions are small enough so that Matthiessen&apos;s rule applies, then it follows from the previous discussion that /3 again will remain equal to Po. If the effect of fatigue is to produce cold-worked regions which are macroscopic—of the order of at least several electron mean free paths—the effective resistivity, p, has to be computed by use of the ordinary laws of large-scale electrodynamics. For the sake of simplicity, it will be assumed here that the cold-worked regions are completely disordered and have a resistivity, p,. For a given proportion A of disordered regions the effective resistivity, p, for the current in a given direction depends on the geometrical configuration of these regions. In any case, the value of p for such

Jan 1, 1956

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.&apos; and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult&apos;s law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry&apos;s law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry&apos;s law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite&apos;" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,&apos; is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors&apos; sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By Robert A. Rapp

The standard molar free energy of formation of MOO,was determined between 750o to 1050o C in galvanic cell measurements involving the solid electrolyte Zr0.85 Ca0.15 O1.85. Use of the reference electrodes Fe + FexO and Ni + NiO Provided two independent determinations of FoMoo2. The data may be represented by the equation FMoO2 = -137,500 +40.0T(°K) which is in good agreement with previous CO/CO, gas equilibrium measurements of Gleiser and Chipman. The standard molar free energy of formation of molybdenum dioxide has recently been reported over a large range of high temperatures from the calorimetric experiments of King, Weller, and christensen.&apos; Gleiser and chipman2 have also recently determined ?FmoO2 from 926o to 1068oC in CO/CO2 gas equilibrium measurements. Earlier gas equilibrium studies have been made and reviewed by Gokcen.&apos; Over the temperature range studied by Gleiser and Chipman their values for ?FoMoO2 differed from the calorimetric data by about 700 cal. This investigation was undertaken to resolve this difference and thereby establish the two phase mixture of Mo + MOO, as an electrode of well-known oxygen potential for galvanic cell applications at very high temperatures. The galvanic cell technique involving the Zr,.,, Ca,0.15 01.85 solid electrolyte was introduced for the

Jan 1, 1963

By P. A. Fisher, J. B. Wilson, D. J. Whitehead, C. J. P. Ball, A. C. Jessup

The properties of a new magnesium alloy ZT1 containing 3.0 pct Th, 2.5 pct Zn, 0.7 pct Zr are described. The alloy possesses good creep and fatigue resistance up to 650°F, is free from microporosity, and is readily sand-cast. ZT1 is shown to be superior to zinc-free Mg-Th-Zr alloys. THE advent of the jet engine created a demand for a light sand-casting alloy capable of being cast into large complex shapes and capable of resisting creep at temperatures up to 500°F. This demand has been largely met by alloys of the magnesium-cerium mischmetal-zirconium types, containing about 3 pct Ce mischmetal and 0.7 pct Zr, typified by Elektron magnesium alloys MCZ and ZREI, the latter alloy also having a zinc addition of 2.5 pct. These alloys utilize the valuable properties at elevated temperatures conferred by the addition of rare earth metals to magnesium, a fact which has been known for many years and discussed by several investigators.1-1 Murphy and Payne8 showed that the addition of the powerful grain-refining element zirconium to Mg-Ce mischmetal alloys produced alloys with attractive room temperature properties combined with good creep properties and castability. With the increasing power of modern jet engines the temperatures to which some of the magnesium parts are subject are likely to exceed the safe working range of the cerium-mischmetal-containing alloys, and at the beginning of the research considerable interest had been shown by aeroplane engine designers in a magnesium sand-casting alloy suitable for service at higher temperatures, e.g., 600°F and above. At an early stage in the development of this type of alloy a check on the fatigue properties at elevated temperatures indicated that, since the fatigue limit even at 108 eversals was appreciably higher than any permissible creep stress, the main emphasis of the research could be concentrated on creep behavior. The primary aim in developing the new alloy has therefore been to attain maximum creep resistance; but due consideration has also been given to other important properties such as castability, tensile strength, and cost. It is by now well established that it is not possible to correlate creep strength with other short time mechanical properties such as are obtained in tensile

Jan 1, 1954

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,&apos; which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins&apos; calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By Leonard Bernstein, Harry Bartholomew

MANY of the properties of metals and alloys are structure dependent. Not the least of these is the grain structure. For example, in producing alloy bonds between silicon or germanium and gold-alloy foil at temperatures above their eutectics (which are, respectively, at 370" and 356°C) but below the melting points of the individual constituents, it was found that wetting was more complete with a fine-grain structure than with a coarse-grain structure. In cases where the assemblies were held together for long periods of time at elevated temperatures, wetting was not as critically dependent on the grain structure as was the case for shorter periods of time. When liquid phase forms, it first forms in the grain boundaries due to the fact that most of the impurities are concentrated at the grain boundaries and that most impurities tend to lower the melting point of the gold alloy somewhat. In addition, grain boundaries are at high-surface free-energy levels and are thus in a more favorable condition to initiate good wetting. A fine-grain structure will have more grain boundaries per unit area than coarse-grain structure thereby making wetting somewhat easier. To make the grain structure of an alloy sys- tem visible, a satisfactory method for differentiating between the different grains of which the system is composed must be employed. For the alloy bonding system previously described, the grain structure on the foil surface is of primary interest. Conventionally used etchants for the gold-alloy system will not adequately delineate grain boundaries in their structures. For this reason an alternate method is proposed for those cases where such a determination is necessary. Foil between 0.0005 and 0.005 in. thick has been used in this determination. The equipment used in this investigation was described in a previous publication.&apos; Essentially, it employs a resistance-type filament which can be heated up very rapidly and cooled very rapidly. A thin refractory material is placed on top of the heating element. This refractory material may be molybdenum, tantalum, tungsten, or even ceramic but its thickness should be less than 0.010 in. to minimize the temperature gradient across it. The gold-alloy foil is placed on top of this refractory material. The temperature of the heating filament is raised to 900°C and cooled down to below 100°C in 5 to 10 sec. During this cycle, the foil can be observed to plastically deform due to its own weight. With no further chemical etching, this assembly is then viewed under a standard metallurgical microscope and the grain size measured. Fig. 1 is a Au-1 pct Sb alloy at 400X magnification and Fig. 2 is a Au-1 pct Ga alloy at 130X. This technique has proved to be an adequate means for controlling processing conditions in producing large quantities of gold alloy foil.

Jan 1, 1963

By F. V. Lenel, G. S. Ansell, J. A. Dromsky

The growth of aluminum oxide particles in a nickel matrix was studied eve?. the temperature vange of 2140° to 2470°F. The instability of the dispersed alumina was shown to be independent of the crystal structure of the alumina. The activation energy for the growth of the dispersed alumina was found to be 84.7 1 2.0 kcal. The particle radius increased as a function of time. These results indicate that the growth is not diffusion controlled. It is believed that the rate controlling mechanism is the dissolution of the aluminum and oxygen atoms into the nickel lattice. THE strength properties of alloys which consist of a finely dispersed second phase in a metallic matrix depend upon the spacing between the second phase particles. It is therefore desirable to achieve very fine dispersions in these alloys. Furthermore, to retain the properties these very fine dispersions must be stable during fabrication and service of the alloys. The best known of the dispersion strengthened materials, the SAP type alloys, which consist of a dispersion of aluminurn oxide in aluminum, have exceptionally good stability up to the melting point of aluminum. There is evidence, however, that other dispersion strengthened alloys, even those consisting of refractory oxides in a metal matrix, may be less stable. This investigation is concerned with the stability of Ni-Al2O3 alloys in the temperature range in which these alloys are usually fabricated. The mechanical properties of Ni-Al2O3 alloys at elevated temperatures have been previously investigated by Crelnens and rant,&apos; and Gregory and Goetzel.2 The behavior of these alloys in stress rupture tests appears to indicate that at temperatures below 1800°F they are highly stable. There is some doubt, however, as to their stability at the higher temperatures used during the conventional fabrication. Cremens and Grant, in preparing their test alloys, cousolidated, by powder metallurgical techniques, nickel powders as fine as 0.13 µ diam and alumina powders as fine as 0.018 µ. Metallo- graphic examination of the alloys following fabrication revealed that none had interparticle spacings of less than 2 µ. Considering the size of the original component powder particles, it is likely that the dispersions coarsened during fabrication. Gregory and Goetzel, in their studies of extruded alloys of 80 pct Ni—-20 pct Cr matrixes with nonmetallic dispersion, observed a definite coarsening of the alumina dispersions in alloys sintered at 2280°F as cantrasted to those sintered at 2000oF. Similar observations on the spheroidization and growth of thoria particles finely dispersed in a nickel matrix were made by D. K. Worn and S. F. Marton.3 As a result of such coarsening, much of the effort expended in the preparation of very fine powder mixtures would be lost. The mechanical properties of the alloys which had experienced coarsening would be expected to be poorer than if the original dispersions had been retained. EXPERIMENTAL PROCEDURE Ni-Al2O3 alloys were produced from powder prepared by a coprecipitation technique. Aluminum hydroxide and nickel hydroxide were coprecipitated from chloride solutions of the metals. The mixed hydroxides were calcined to form metal oxides and the nickel oxide in the mixture was selectively reduced to nickel by treating it in hydrogen. Specimens were compacted from the resultant powder which consisted of a fine, uniform mixture of aluminum oxide and nickel particles. The compacts were sintered by resistance hot pressing4, a densification technique which requires exposure times of the order of only a second or less at elevated temperatures. A conventional sintering process was not used, since the temperature required for densification would have to be in the region in which the stability of the dispersion was to be studied. A series of hot pressed specimens were treated in hydrogen at temperatures from 2140o to 2470°F (1171o to 1355oC, for times up to 120 hr. Changes in the microstructures were studied by electron microscopy using the two-stage preshadowed carbon replica method.5 In performing a lineal analysis on a series of micrographs from each specimen it was found more convenient to determine the mean free path between alumina particles rather than particle radii as the parameter of growth. Although these quantities are directly proportional for only spherical particles, the alumina particles in these alloys

Jan 1, 1962

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil&apos;chenko&apos; found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli&apos; bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil&apos;chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.&apos; The presence of silicon in iron is said to reduce the activation energy for diffusion,&apos; so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen&apos; made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957