Search Documents

By H. I. Aaronson, S. M. Kaufman, G. M. Pound

WHETHER the carbides associated with bainite precipitate from the ferritic component of bainite, as originally suggested by Davenport and Bain, or from the adjacent austenite at aus-tenite:ferrite boundaries, as proposed by Hultgren, 2 remains in dispute.3-5 A recent metallographic investigation in this laboratory has shown that the bainitic carbides formed in a plain carbon hypo-eutectoid steel nucleate entirely within ferrite at higher reaction temperatures3 and in both ferrite and austenite at lower temperatures." The present investigation was undertaken to ascertain the effects of alloying elements on the nucleation sites selected by bainitic carbides. The compositions of the steels studied were as shown in Table I. Specimens of these steels were

Jan 1, 1958

By S. F. Reiter, R. W. Guard, J. H. Keeler

DURING the last several years the authors have been conducting tests on a tensile machine that autographically records load-elongation data. In certain tests at elevated temperatures on face-centered cubic, hexagonal close-packed, and body-centered cubic materials (binary alloys of nickel, zirconium, and iron), the load-elongation curve as shown in Fig. 1 reaches a maximum load (Pmax,) at relatively small amounts of strain and a large amount of elongation occurs subsequently with a continuously decreasing load, until finally localized necking and fracture take place. This early maximum load behavior has been found without the accompanying evidence of localized necking as has been assumed by some, or of evidence of cracking as observed by others.' This behavior has also been observed by Nadai and Manjoinez whose results are in good agreement with ours. The prior strain, strain rate, test temperature, and crystal structure affect the observations. The influence of prior strain was observed in tests on unalloyed zirconium at 300°C in which specimens containing large amounts of prior strain (cold work) exhibited the type of curve shown in Fig. 1. No localized necking was observed after strain as much as that of point B. Annealed and recrystallized specimens of the same material showed a load-elongation curve with maximum load occurring after considerable strain hardening and at the beginning of localized necking. Interrupted tests (Fig. 2) show no loss in strength because of recovery or recrys-tallization during an interval at temperature without load. Recovery under stress such as found by Wood and Suiter3 in aluminum is now being investigated as one possible explanation. The strain rate is a contributing variable as shown in Fig. 3, a test on high purity nickel. Here the strain rate was decreased by a factor of ten during a test in which the maximum load was reached at a small strain. The slope of the true stress-true strain curve was positive with the more rapid strain rate and negative with the slower strain rate. In many binary ferrites an added effect of temperature has been observed. Fig. 4 shows the load-elongation plots for a binary ferritic alloy containing 2 pct Mo. The slope of the small portion of the stress-strain curve obtained at a strain rate of 0.01 mhr1 changes sign from negative to positive on going

Jan 1, 1955

By W. Rostoker

PART of a program of research on the Ti-A1 system1 involved a study of the lattice parameters of the titanium-rich a solid solution, which has a hexagonal close-packed structure. For this work, a 14 cm Debye-Scherrer powder camera and filtered CuK, radiation was used. For each pattern, the parameters were calculated by a least squares solution of the five strongest high angle lines. This provides an accuracy of i0.005A or better. The results are shown graphically in Fig. 1. It will be seen that an unusual change of slope occurs in the curve for the C parameter at high aluminum contents. Such anomalous changes in slope have been recorded by RaynorV or several magnesium-rich solid solutions. The effects were interpreted in terms of a special contribution to the lattice distortion due to factors of electronic origin predicted by Jones." Jones' theory, in substance, suggested that an unusually large expansion of the lattice would begin when the electron per atom concentration in the alloy was increased to a value at which an overlap just began from one Brillouin zone to another. Con-

Jan 1, 1953

By W. Rostoker

LAVES and Wallbaum1 and more recently Duwez and Taylor' have reported on the occurrence of a family of intermediate phases having the composition Ti2X, where X may be Cu, Ni, Co, Fe, or Mn.

Jan 1, 1953

By R. P. Carreker, R. L. Fullman, J. C. Fisher

THE existence of the phase TiAg has not been reported previously. Other investigators have denied the existence of compounds in the Ti-Ag system.13' However, phases of equi-atomic proportion have been reported by Raub, et al.' in the (similar) systems of titanium with gold and copper and zir- conium with silver. Raub's work indicated that titanium and silver are immiscible in the liquid state. No evidence of this was found although a very wide melting range exists which makes the preparation of homogeneous alloys difficult. TiAg is apparently formed by a peritectic reaction between /3

Jan 1, 1954

By R. R. Morral, F. M. Krill, K. T. Aust

THE occurrence of twins in aluminum ingots cast under certain conditions has been well established. For instance, Herenguel and Lacombe1,2 have observed a twinned columnar structure in 99.5 and 99.9 pct Al, solidified by continuous or semicontinuous casting. The structure, which they termed "basaltic," appears in the form of elongated crystalline fibers of alternating luster. Herenguel and Lacombe2 found sections of flat crystalline plates composed of twin crystal plates, in which the twin plane (111) and a [I121 direction contained in the twin plane are parallel to the principal heat gradient. This orientation relationship is different from the usual orientation texture observed in cast face-centered cubic metals, where the [100] direction is approximately parallel to the long columnar axes lying in the direction of growth." A large amount of twinning has also been observed by the present authors in semicontinuous cast aluminum of 99.2 pct purity, Fig. 1. Mondolfo4 has suggested that the twinned cast structure forms by a deformation twinning process as the result of uneven cooling stresses within the ingots. This suggestion appears to be inconsistent with the large amount of twinning observed in the semicontinuous cast ingots and with the large difference of dendritic

Jan 1, 1953

By R. A. Bloom, John Birtalan

CONSIDERABLE interest has been shown in recent years toward determining the crystal structure, mode of formation, and chemical composition of the x phase, designated as such by Andrews,' who was the first to establish its presence in Fe-Cr- Ni-Mo alloys . Later work2 by the same author has shown that the occurrence of x depends on the presence of some molybdenum in the alloy. The phase, which appears to be identical or very similar to a manganese, has a body-centered-cubic structure and is closely related to s phase. Koh observed a similarity in composition between x and s and speculated as to whether x might be an ordered structure of u which is known to have a tetragonal crystal

Jan 1, 1957

By O. P. Arora, J. B. Darby, Paul A. Beck

LAVES and Wallbaum' reported that the phases occurring at the compositions TiFe, TiRu, and TiOs, which are stable over a wide range of temperatures and are separated from neighboring phases by wide two phase fields, have a CsC1-type ordered structure. For TiRu and TiOs, this was recently confirmed by C. B. Jordan.2 Recent results of Greenfield and Beck3 show that solid solutions with ruthenium of the body-centered-cubic elements vanadium and tantalum (and presumably also of colum-bium) in group Va of the periodic table undergo CsC1-type ordering. Although detailed phase diagrams for these systems are not yet available, it would appear that these ordered structures are separated from the neighboring body-centered-cubic solid solutions by relatively narrow two phase fields.

Jan 1, 1957

By J. Chipman, J. C. Fulton

BECAUSE of the great importance of the ternary system Fe-C-Si in ferrous metallurgy a considerable amount of attention has been devoted to the phase relations, particularly those occurring in the solid state.' The information on graphite solubility

Jan 1, 1955

By Tormod Forland

FROM equilibrium measurements on the system NaF-Na 3A l Fo-A 1 2 O 3-Na CO 3-CO 2 with high contents of NaF, Forland, Storegraven, and Urnesl concluded that complexes are formed containing two oxygen, three aluminum, and a less defined number of fluorine per complex. The same number of oxygen atoms per complex was also found by cryoscopic measurements for mixtures high in NaALF 6. In a recent paper by Stokes: some other complex ions, Al2O2F42- and AlOF2-, have been suggested. Here an additional argument in favor of the complex ALO2F. suggested by Forland, Storegraven, and Urnes will be given. When fused Na3AlF6 containing some A12O3, is cooled slowly, the solid phase will consist of the two components as separate phases. The melting point and the heat of fusion of Al2O3 are so high that this component will form the stable solid phase even though in the liquid state the complex may have a high stability. If, however, the fused mixture is quenched, the decomposition of the oxygen-containing complex and the formation of solid Al2O3 does not proceed fast enough, and a solid solution of A12O3 in Na3AlF6 is obtained. Zintel and Morawietz3 obtained cryolite containing 10 pct AL2O3 in this way. The density and the lattice parameters of the A12O3 containing cryolite were also measured, and from this it was concluded that the Al2O3 enters the cryolite lattice as Al3AlO0 groups replacing Na3AlF6 groups. However, the experimental data could as well be explained by assuming that one Na+ ion and two of its neighboring F- ions are replaced by one Al3+ ion and two O2- ions. This may be pictured schematically as: F F F F F F F Al F Na F Al F ,-Na+ + Al8+ F Al 0 A1 0 A1 F F F F —2 F- + 2O2- F F F solid cryolite cryolite-alumina solid solution This means that the complex in the solid solution, derived from X-ray and density measurements, is the same as that which Forland, Storegraven, and Urnes derived from equilibrium measurements in the liquid state. References IT. Forland, H. Storegraven, and S. Urnes: Ztsch. fur anorgan-ische und allgemeine Chemie, 1955, vol. 279, p. 205. 2J. J. Stokes: AIME Trans. To be pubhshed. s E. Zintel and W. Morawietz: Ztsch. pubhshed.fur anorganische und allgemeine Chemie, 1939, vol. 240, p. 145.

Jan 1, 1958

By H. T. McAdams

Current theories of fracture maintain that brittle materials contain flaws or regions of weakness at which fracture originates. Whether a particular flaw grows depends upon the stress distribution in its vicinity and upon the presence of other stress relieving mechanisms capable of absorbing the applied energy. Under load, therefore, certain of these flaws will be activated, and the resulting fragments will have a size distribution determined by the spatial distribution of active flaws. Gaudin and Meloy,1 assuming a random occurrence of flaws, have derived the size distribution of fragments as

Jan 1, 1965

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By W. H. Smith

IN the course of an investigation on chromium containing minor amounts of alloying elements, the information herein has been obtained on the crys-tallographic orientations resulting from arc melting, rolling, and annealing. The chromium used in this investigation was electrolytic flake obtained from the Electro Metallurgical Co. This material was heated for 20 hr at 1600°C in hydrogen with a dew point of about — 100°C. The oxygen and nitrogen content of the chromium after this treatment was 0.0003 pct 0 and 0.005 pct N. Five pounds of this chromium were arc melted in a water-cooled copper crucible. After arc melting, the oxygen and nitrogen contents were 0.002 and 0.025 pet, respectively. A section of this ingot is shown in Fig. 1. By means of a back-reflection Laue technique, the crystal habit of the cast ingot was determined. As expected, it was found that the [loo] was approximately the axis of the columnar grains. In this respect, chromium behaves like other body-centered-cubic metals in that a cubic axis is normal to the cold surface of the mold. A slab cut from this ingot was rolled at 600°C as follows: four 30 pct reductions were made with intermediate anneals at 1200°C for 15 min. Rolling was done with the [loo] of the columnar grains in the rolling direction. Following the final anneal, an 80 pct reduction was taken at 600 °C. The final sheet thickness was ten mils. By polishing and etching, the thickness was reduced to four mils and the grain orientation determined by the transmission Laue method using molybdenum radiation with a zirconium filter. Fig. 2 is the (110) pole figure for this material with the ideal (100) [011] and (111) [112] orientations indicated. The orientation is typical of most cold rolled body-centered-cubic metals having the [llO] of the grains approximately in the rolling direction and the (100) planes approximately in the plane of the rolled sheet. There is also evidence of some 10) [1 orientation. The grain orientation of sheet rolled 40 and 80 pct in the same direction as before at 600°C followed by recrystallization at 12000 C for 15 min was determined by a back-reflection Laue technique. A random texture was found in both cases. This 1200°C 15 min anneal was found to give complete recrystallization and some grain growth.

Jan 1, 1956

By M. B. Bever, A. B. Michael

THE structure of cast A1-Si alloys is altered profoundly by modifying agents. Sodium, in particular, reduces the size of the silicon particles in the eutectic and tends to change their shapes from plates to nearly rounded grains. This refinement is accompanied by a shift of the eutectic to higher silicon concentrations and lower temperatures. Similar effects can be attained by rapid solidification. Hypotheses advanced to explain modification have involved the formation of a ternary eutectic,1 the removal of oxides by fluxing,' and even a presumed allotropic transformation of silicon. Other hypotheses assume that the modifying agent causes an envelopment of the silicon particles by the aluminum-rich solid solution, but attribute this envelopment to different mechanisms. According to various explanations, the growth of the silicon particles is obstructed by an immiscible sodium-rich liquid," an adsorbed layer of sodium,' or a ternary compound;5 his obstruction has been conceived as purely mechanical or as a colloidal action.' It has also been proposed that sodium reduces the surface tension on the Al-Si interface, thus permitting the aluminum-rich solid to grow faster and to envelop the silicon particles.? Still other hypotheses stress undercooling and the attendant change in the rate of nucleation of silicon, but fail to ascribe any definite function to the sodium addition." '" Procedure High-purity alloys of aluminum and 3 or 7 pct Si were treated with modifying agents containing radioactive sodium tracers. The experiments were intended to investigate the partition of sodium between the primary aluminum-rich solution and the eutectic, and, if possible, to determine whether sodium is concentrated in or around the silicon particles in the eutectic. Radioactive sodium fluoride, alone or mixed with stable sodium chloride, was allowed to react with the alloy for 5 min immediately before solidification in the crucible. Modification could not be attained with additions of less than the equivalent of approximately 0.1 pct Na. Some alloys were not completely modified, but comparison of the structures of treated and untreated specimens indicated a very considerable reduction in particle size of the silicon in all of the former. A treated alloy is shown in Fig. 1. Radioactive sodium fluoride was prepared by bombardment with deuterons having an energy of 14 mev. This bombardment (totaling, for example, 6 microampere-hours in one run) produced radioactive Na24 (half-life 14.8 hr) by the reaction 11Na23 (d,p) 11Na24. The radioisotopes of fluorine also produced have short half-lives and were not detected. A half-life determination by counting confirmed that the measured activity was due to Na24. The distribution of the sodium in the solidified alloys was determined by an autoradiographic technique by which a suitable stripping film is attached to a very thin metallographic specimen. After exposure and development, this emulsion remains superimposed on the specimen and may be examined microscopically or photographed by reflected light. The emulsion of the autoradiograph can be correlated directly with the underlying surface by simple adjustment in focus. The details of this technique have been described elsewhere." Results Fig. 2 is a micrograph of the autoradiographic emulsion ("autoradiograph") lying directly above the area of eutectic in Fig. 1. Fig. 3 shows a similar autoradiograph of a region consisting of primary solid solution. The small black dots (tracks) in these autoradiographs are developed grains in the emul-

Jan 1, 1954

By R. E. Maringer, A. Schwope

IT has been recognized that oxygen in minute quantities is extremely detrimental to the room-temperature ductility of molybdenum. Early fracto-graphic studies' of the cast metal indicated that oxides are formed preferentially at the grain boundaries. Additional verification of this preferential segregation has been obtained from internal friction studies on poly crystalline molybdenum (average grain diameter varied from 0.039 to 0.065 mm) and from observations of the effect of oxygen on specimens of extremely large grain size. Specimens A, B, and C, of 0.040 in. diameter commercial molybdenum wire (Lot FW 13-40) were heat treated in the vacuum furnace described by Few and Manning according to the specifications given in Table I. Internal friction studies of these specimens were carried out using a low frequency (approximately 1 cycle per second) torsional pendulum completely enclosed in a vacuum tank. As the pressure of oxygen in the heat treating atmosphere changed, the portion of the internal friction vs temperature curves ascribed to grain boundary relaxation changed correspondingly, Fig. 1. The decrease in the damping capacity at high temperatures as the pressure of oxygen in the heat treating atmos-

Jan 1, 1955

By W. Rostoker, S. Spachner

A N alloy of 50 pct Ni-50 pct Fe is currently manu- factured in tape thickness down to 1/8 mil. In the annealed form, this alloy produces an almost square hysteresis loop. This has generally been related to the fact that by proper rolling and annealing practice a sharp cube, (100) [OOl], texture can be developed. As part of a program directed toward an understanding of the relationships between magnetic properties and structure of tape core materials, analyses were made of preferred orientations in tapes of various thicknesses. Annealed tapes of this alloy in 2, 1, 1/2, ¼, and Y' mil gages were acquired from commercial sources. Pole figures constructed for the 2 and 1 mil tapes showed the expected sharp cube texture. However, the ½, ¼, and ? mil annealed tapes showed no evidence of any preferred orientations. A comparison of two transmission patterns is shown in Fig. 1. The origin of the absence of texture in the tapes of less than 1 mil thickness was explored in some detail. The basic questions were whether the heat treatment for the thinner tapes was wrongly selected, whether the initial cold worked textures were different, or whether the actual thickness of the tape exercised some influence on its annealing characteristics. Quantities of the five gages of tape were acquired in the as-rolled condition just prior to the final anneal. Pole figures of the cold worked textures were constructed for each of the tapes. Eye estimates of in-

Jan 1, 1956

By H. Papazian, Robert A. Lad

SINCE it can be shown both theoretically'' : and experimentally that disordered Cu3Au has a greater internal energy than the ordered alloy, it might be expected that its chemical reactivity would be greater. Experiments were initiated' to test this hypothesis. This note will describe some recent results obtained in the study of the rates of corrosion of ordered and disordered polycrystalline Cu3Au by aqueous FeCl., The work of Robertson' has indicated that the attack by such solutions is intergran-ular and highly orientation dependent. It was of interest to see whether the order-disorder effect was great enough to overcome the variations from specimen to specimen which would arise from this type of attack. The polycrystalline alloy specimens (0.020 in. wire, 1¾ in. long) were preannealed in ½ atm H, at 700°C for 2 hr. The subsequent heat treatments to produce order and disorder were performed in M atm He. Disordered specimens were obtained by heating at 450°C for 2 hr and quenching in water. Ordered specimens were produced by heating for 2 hr at 450°, furnace cooling to 380°, and soaking at 380°C for 80 to 90 hr. Room temperature was reached by cooling to 150" at a rate never exceeding 7" per hr, and water quenching from 150°C. The specimens so produced exhibited electrical resistivities characteristic of the two states; of the order of 11.27x10 ohm-cm for the disordered, and 4.28x10 ohm-cm for the ordered specimens. The corrosion rates were studied at 30°C in ferric chloride solutions of several concentrations (?,¼, 1.5, and 1 molar). The specimens were attached to a stirrer during the tests. Tests were interrupted at intervals, and the specimen weight change was determined after washing and drying. Analysis of the solutions showed that the attack was limited to the copper. The higher corrosion rate for the disordered alloy, as illustrated in Fig. l, is typical of the results obtained. The effect of variation in ferric chloride concentrations is indicated in Table I for typical specimens. The variations in the ratio of reactivity for disordered and ordered specimens at the different concentrations are within experimental error, and the best value is estimated to be near 1.4. The experimental variation was due in part to the mode of attack, as mentioned, and in part to the fact that films were formed on the specimens under some conditions. Electron diffraction patterns of the films were very complex and indicated the presence of metallic iron, as did chemical analysis. In an attempt to eliminate the difficulties arising from the mechanism of attack, single crystal specimens were used. A greater reaction rate was again measured for the disordered specimens, but the reproduci-bility was no better than that for the polycrystalline metal. This would indicate that film formation was primarily responsible. It was concluded that the reaction with aqueous ferric chloride served to demonstrate that the reactivity of disordered Cu3Au is greater than that of the ordered alloy. However, the difficulties with film formation did not permit determinations of a precision great enough to warrant extension of the study to partially ordered alloy systems.

Jan 1, 1957

By C. G. Dunn, F. W. Daniels, M. J. Bolton

Recent observations on grain boundary movements in sihcon iron have indicated the possibility of studying grain growth phenomena in two-grain specimens in which several variables affecting growth are readily controlled. These variables are (1) the energy per unit area (?) in the grain boundary, (2) the orientation relationship of the two grains, and (3) the radius of curvature (7) of the moving boundary. Ideally, one grain A should be a narrow rectangular parallelepiped adjacent to a second grain ß as shown two dimensionally in Fig 1. Such a two-grain group becomes unstable when one end of grain A is shaped according to the dotted line. Since the width w of grain A remains constant during growth of grain B, T should also remain constant. The other vari- ables mentioned above can be controlled in the preparation of each two-grain specimen.l,2,3 For a parLicular orientation of each grain, is not necessarily fixed; ? may also depend on the orientation of the grain boundary, but this may be controlled to some degree. The energy relationships for the gowth of grain ß may be derived from the more simple arrangement of two grains A' and B' shown schematically in Fig 2. Here B' largely surrounds A'. Assume these grains are oriented with a common plane parallel with the flat

Jan 1, 1950

By Wolfgang Gartner

METALLURGISTS engaged in the pulling of single crystals of germanium and silicon, and their zone purification and zone levelling for transistor and diode production, have found that the lifetimes of minority carriers in low resistivity samples tend to be shorter than in high resistivity material, although equal care is taken in the crystal preparation. In other words, it is more difficult to obtain long lifetimes in single crystals of low resistivity semiconductors. It is the purpose of this note to point out that this phenomenon follows directly from the Hall1 and Shockley-Read' theories of lifetimes in semiconductors." In general, the recombination mechanism may be very complicated,' but experiments seem to indicate that the simple formula2 for the lifetime of excess carriers given by n0 + n3 Pn + P1 T = Tpo,------------------+ Tjpu ----------------------- [ 1 ] nu + pn na+ + Pa is a good representation of the situation prevailing in transistor grade semiconductors. In this formula, no and pa are the equilibrium densities of electrons 6+ - E./ET and holes, n1 = N,e is the number of electrons E1- E2/KT in the conduction band, and p1 - N,e is the number of holes in the valence band, both for the case in which the Fermi level falls at the trap level, E1. N,. is the effective density of states in the conduction band; E1, the recombination level; E1, the lower edge of the conduction band; k, Boltzmann's constant; T, absolute temperature; N,., effective density of states in the valence band; and E,., the upper edge of the valence band. t,.,, denotes the lifetime of holes injected into highly n-type material, and The indicates the lifetime of electrons injected into highly p-type material. Eq. 1 holds for nondegenerate semiconductors in which only one recombination level is active and the charge in the recombination centers is neglected. It is further assumed that the number of injected ex-

Jan 1, 1957