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By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By Y. Nakada, E. J. Fasiska, A. S. Keh, L. Zwell

DURING an investigation of solid-solution hardening of nickel by carbon,' we found that there were no reliable data on the dilating effect of dissolved carbon on the unit cell of nickel. Bernier2 reported an increase in lattice parameter of nickel (3.523A) when an unknown amount of carbon was introduced into solid solution (3.536A). Similarly KG, Tsien, and Misek3 found an increase from 3.523 to 3.531A when nickel was carburized. strong4 studied the variation of nickel lattice constant as a function of dissolved carbon. However, in his case carbon was introduced into nickel by solidifying the melt at 65 kbar. Therefore, his carbon concentrations were much above the highest equilibrium solubility limit5 (2.7 at. pct C at 1 atm). Knowledge of the lattice mismatch between solute and solvent is essential in understanding the mechanism of solid-solution hardening. Therefore, we decided to determine the dilation of the nickel lattice by carbon under the more usual conditions of atmospheric pressure. The material used was Inco Electrolytic Nickel of 99.95 pct purity, as specified by the supplier. The impurity contents in wt pct were: Fe, 0.01; Cu, 0.01; Co, 0.03; 0, 0.005; C, Si, S, N, trace. To this base material various amounts of AUC-grade high-purity carbon were added during vacuum induction casting. Ingots, 2 in. in diam, were heated in a muffle furnace at 1000°C for i hr., hot-rolled to 1/2-in. thickness, and quenched into brine. All ingots with carbon concentration greater than 0.98 at. pct were enclosed in a cast iron box during the heating to minimize decar-burization. Small pieces were then either swaged down to 0.028-in.-diam wire or cold-rolled to 0.010-in.-thick sheets. After the final cold reduction in area of 50 pct, the specimens were recrystallized by heating in evacuated capsules at 1100°C for 60 to 80 sec and then quenched into brine. The final grain size was 50 to 100 µ. The carbon contents of the alloys, Table I, were determined by a combustion method

Jan 1, 1969

By Y. Mishima, R. Shiromizu

THE equilibrium y phase in Cu-Be alloys forms by discontinuous precipitation, the new phase nucleating at the grain boundaries and growing into grains on both sides of the boundary. When the alloy is aged above 500°C, however, growth may take place into only one of the grains.1'2 In A1-Ag alloys it is known that the precipitate has the same orientation as the grain in which no growth takes place.3, 4 This was confirmed in the present investigation on a Cu-Be alloy. A Cu-1.79 wt pct Be alloy was solution-treated at 810°C for 2+ hr, quenched into water at O°C, and aged at 600°C for 1 hr in a salt bath. The specimen was thinned by chemical polishing and electropolishing at room temperature in a solution of H3PO4 saturated with CrOs. The foil produced was examined in a JEM 150 electron microscope operating at 150 kv. Fig. 1 shows precipitates growing on only one side of the grain boundary. The black platelike precipitates were identified as the y phase. Electron dif-

Jan 1, 1969

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy's obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:'l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By D. A. Woodford

A number of observations have now been reported where the steady-state creep rate is apparently linearly dependent on the applied stress at high temperature and low stresses. This results in a creep rate greater than that predicted by extrapolation of high-stress data and has obvious practical implications. However, some of these observations are open to question. For example, the analysis by Harris and Partridge17 of the data of Greenfield et a1.18 was dependent on strain rates which, according to the original authors, were too low to be measured. Dr. Bernstein appears to have demonstrated a linear stress dependence at low stresses in two zirconium alloys. There are, however, a number of discrepancies in his treatment of the data and the subsequent theoretical analysis which require clarification. 1) It is incorrectly stated that steady-state conditions are revealed by a slope of unity on a plot of log i vs log (time). This objection is trivial if the author meant to say a slope of zero, although it is unclear how subsequent extrapolation was made to determine the steady-state creep rates at low stresses for the zircaloy-2. If the plot used was actually log c vs log (time), it is unlikely that a slope of unity would represent a constant creep rate. A plot of log (c - co) vs log (time), where c0 is the extrapolated intercept sf the steady-state creep rate on the strain axis, would have a slope of unity during steady-state creep. However, eo cannot be determined unless is is already known. 2) The author chooses to interpret his results based on the equation: where A, and B, are structure-sensitive parameters, Ql and Q, are the activation energies for the particular creep process, and n describes the sensitivity of the creep rate on stress. The first term represents a slip creep process and the second a diffusion creep process. However, it is stated later that "two distinct processes acting in parallel are involved". Eq. [I] surely represents two processes in series since each reacts to the total applied stress and t, is the sum of the individual creep rates. If the processes are acting in parallel, then the effective stress in each would be less than the applied stress. The component stresses would be given by sl + s2 = a but it is not clear how the magnitude of either, or the corresponding stress exponent, could be determined.

Jan 1, 1969

By J. R. Cahoon, W. V. Youdelis

In a recent publication by Flemings and Nereo, equations for the calculation of the solute distribution in castings were developed, and the solute distributions for unidirectionally solidified A1-4.5 pct Cu ingots cast under various thermal conditions were calculated. The equations derived by Flemings and Nereo for the dendrite "expansion" and "steady-state" zones are essentially equivalent to those previously published by Kirkaldy and Youdelis, 16 for, although the flow velocity cooling rate, and temperature gradients appear in the fundamental differential equations, calculation of the solute distribution requires that the above be explicitly related to the assumed or measured solid-liquid mass distributions during solidification. In the treatment of Kirkaldy and Y-oudelis the mass distributions are simply assumed or measured without any prior and explicit association of the mass distributions to a velocity parameter. The treatment of Flemings and Nereo permits solidification conditions more complicated than the simple unidirectional case to be considered (although in principle the treatment of Kirkaldy and Youdelis could also be extended to include the more general solidification case); however, we note some limitations in the treatment of Flemings and Nereo, and the purpose of this discussion is to point these out and also to indicate those points of similarity in the mass distribution models used which make the two treatments equivalent. Both the Kirkaldy-Youdelis and Flemings-Nereo treatments consider a zone of dendrite "expansion" followed by a "steady-state" zone. However, Flemings and Nereo have failed to consider a zone of "collapse" which begins at the base of the first dendrites to reach the top of the ingot. The omission of this zone of "collapse" results in too high a value for the solute concentration in the latter portion of the ingot to solidify and the conservation of total solute is not possible. In the zone of "collapse" the solute concentration rapidly decreases, which may be accounted for as follows: consider a mushy zone of length X,, shown schematically in Fig. 11 (a), which develops at the chill face and then moves as a steady-state configuration along the length of a solidifying ingot. The solute distribution in this zone, when it first attains the steady state, is shown qualitatively in Fig. 11(b). The segregation is positive (above Co) in the region ab because this region contains primary dendritic solid, ranging from kco to kcE in composition (where k is the partition coefficient and CE is the composition of the eutectic liquid), and liquid metal near eutectic composition. The segregation is negative (below Co) in the region bc because it contains primary dendritic solid only slightly above kco in average composition and liquid metal only slightly above Co in composition. As the zone X, moves as a steady state

Jan 1, 1969

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By F. A. Crossley

The key to disagreements between Blackburn's findings and mine is the word equilibrium". My work attempted to define the equilibrium diagram of the titanium-rich end of the Ti-A1 system. It can readily be shown that Blackburn's conclusions are based primarily on the examination of structures substantially removed from equilibrium. The diagram presented in Fig. 16 is properly labeled a "phase diagram". However, it appears that Blackburn either does not understand or does not accept the difference between "phase diagram" and "equilibrium diagram" as defined in the Metals Handbook.17 The conflict lies not in Blackburn's data but in his interpretation of it, and his use of "transformation", "phase diagram", and "equilibrium diagram" as synonymous terms. I share his view that the light microscope is much inferior to the transmission electron microscope for the study of transformations; but this fact does not render the light microscope useless or untrustworthy. The difficulties experienced with the Ti-A1 system have not been due to the limitations of the light microscope, but rather to the extreme sluggishness in achieving equilibrium at temperatures below 1000° C. Were it not for the light microscope employed with polarized light, the twin phase syndrome' might still be unrecognized and, as a consequence, still adding to the confusion of Ti-A1 investigations. (Ref. 1 should read ... Contract No. N161-25952 ... vol. 236.) Other, more sophisticated techniques, including electron transmission, simply confirm the erroneous tentative conclusions drawn from observations of structures due to the twin-phase syndrome. By the standards of most of the investigations of the Ti-A1 systems, seven of the fifteen compositions investigated by Blackburn were seriously contaminated with oxygen. The writer has found that 0.1 wt pct 0 shifts the a + Ti3A1 boundary to 1 at. pct lower A1 content at 700°C. At constant aluminum content, this corresponds to a temperature shift of the boundary of +25°c.18 Blackburn advises that the first group of alloys contained 0.1 to 0.15 wt pct 0, bur he does say whether the analyses were performed on as-received material or on specimens in their final state of heat treatment. This is especially important considering the 20-mil-thick starting materials. If specimens had been annealed in the two-phase a + 6 region it would have provided an indication of the final degree of oxygen contamination since up to about 12 at. pct A1 the boundaries of this region are well-defined for low-oxygen alloys. Blackburn questions the capability of light microscopy in determining phase boundaries in the Ti-A1 system. I submit that the a/a + Ti3A1 boundary in Fig. 1 of Ref. 1 over the composition range from 10 to 18 at. pct A1 was determined by dilatometry and supported by electron diffraction. Specimens of alloys containing 8, 10, 12, and 14 at. pct A1 were aged at 550°C for 1000 hr (under stress of 5000 psi to accelerate the tendency to equilibrium) and then fractured in tension at room temperature. Collodion was applied to the as-fractured (unetched) surface and, when stripped, carried away particles identified by electron diffraction as Ti3A1. Perhaps Blackburn will explain why these electron diffraction data were ignored. At this time, a technique for revealing or indicating

Jan 1, 1969

By R. C. Gifkins

The ideas expressed in this paper interest me very greatly, partly for their own sake and partly because they are very close to some speculation I have recently made concerning grain boundary diffusion. This is in a paper describing an extension to Mott's "island" theory of the grain boundary, to be published shortly.37 The facets or islands of good fit are identified in terms of specific crystallography, as in the model put forward by Brandon et al., and the bad fit between them is suggested to be interlinked "channels" of relaxed vacancies, associated with grain boundary ledges.

Jan 1, 1969

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

By M. J. Hordon, M. A. Wright

ReCENT work has indicated that the substantial decrease in the rate of fatigue crack propagation for aluminum observed below a critical vacuum level can be attributed to the depletion of oxygen or water vapor from the vicinity of the fatigue crack opening.' At reduced gas pressures, generally below 10-2 Torr with fatigue strain amplitudes in the range *1 to 2 x 10-3 and cyclic loading rates of 25 to 50 cps, estimated rates of oxide or hydroxide monolayer adsorption on newly formed crack surfaces can fall behind the actual rate of crack extension. Changes in the critical pressure required for the transition in fatigue behavior with changes in temperature, strain amplitude, and cyclic frequency can be interpreted from variations in the adsorption and crack growth rates.'" Although the adsorption model generally appears to explain the enhanced fatigue resistance of reactive metals in vacuum, the specific adsorbing gas species and nature of the adsorption mechanism are uncertain. In addition to the direct dissociation and adsorption of O2 on the metal surfaces,3 the dissociation of H20 and subsequent adsorption of H ions have been advanced for aluminum alloys.4 The present note describes some measurements of the fatigue behavior of 1100 aluminum in reduced partial pressures of specific gases including O2, H2O, and H2 in order to provide additional experimental data. Cantilever-type specimens of 1100-H14 aluminum were fatigued in cyclic reverse bending at constant strain amplitude using a multispecimen vacuum apparatus and procedure described previously.' After initial vacuum evacuation to 1 x 10-7 Torr, the appropriate gas species was bled into the system through a calibrated leak valve. The input rate was adjusted to maintain the desired pressure level under continuous evacuation, thus minimizing possible changes in gas composition during testing. High-purity input gases including 99.9 pct O2, 99.999 pct H 2, and water vapor from triply distilled H 2 O were used to provide residual pressures. Trace amounts of contaminant species were limited by passing the Oz and H 2 input gases through liquid-nitrogen-cooled copper coils prior to entry to the test chamber. Care was taken to repeatedly flush the gas lines and valves before testing to minimize the effect of adsorbed contaminants. Residual gas pressures in the range 10-6 to 5 x x3 Torr were monitored by an NRC ionization gage corrected for each gas species. In the higher-pressure range, 5 x 1CT3 to 5 x 10' Torr, an NRC alphatron gage was used. In operation, eight simultaneous fatigue tests were conducted at a constant strain amplitude of *1.2 x 10 at cyclic bending rates of 25 and 50 cps to give an average fatigue life of 6.5x 105 cycles-to-fracture at standard atmosphere and 3.3 x 106 cycles in 1 x 10"7 Torr vacuum. Representative results for the effect of residual O2, H2O, and H2 contents on the fatigue life are shown in Fig. 1 for tests performed at 50 cps. It is apparent that the presence of either O2 or H2O gas in the system at partial pressures greater than 10"3 Torr was noticeably detrimental to the fatigue life. In contrast, the enhanced fatigue resistance typical of high-vacuum environments was retained with pure H 2 through the pressure range up to 1 Torr. For partial pressures of H2 gas above 1 Torr, the fracture life noticeably decreased. The critical Hz

Jan 1, 1969

By R. K. Datta, T. S. Davis

YVO4:EU, excited under 3650A radiation, shows a marked increase in total brightness with in~rease in temperature. At 25°C the response to 3650A radiation is about 48 pct of its maximum response which occurs at about 350°C, Fig. 1. In an attempt to explain the phenomenon, one of the present authors' (R.K.D.) investigated the diffuse reflectance spectra of the phosphor at different temperatures (up to -150°C) and was unable to observe any significant change to which the increased brightness could be reasonably ascribed. Since then diffuse reflectance spectra at elevated temperatures have been obtained in this laboratory using an improved device. A significant decrease in the diffuse reflectance of a phosphor in the ultraviolet region—especially in the longer wavelength region—at -300°C has been observed. The purpose of this note is to describe the device used for high-temperature reflectance measurements and to explain the increased brightness of YVO4:Eu phosphor at elevated temperatures under 3650A excitation. Experimental. YVO4 and YVO4:Eu samples were prepared as previously described.' The elevated-temperature reflectance spectra were obtained with a Cary 14 spectrophotometer equipped with a diffuse reflectance accessory and a ring collector. CaF2 was used as the standard. The cell used

Jan 1, 1969

By H. I. Aaronson, H. A. Domian, A. D. Brailsford

A current study of the growth kinetics of k (hcp) plates in a Cu-Si (fcc)' has generated a requirement for data 02 the chemical interdiffusion coefficient in a (termed D,) as a function of temperature at the composition of the a/a + k pJase boundary. Rhines and Mehl 2 have determined D, as a function of composition at lower silicon contents by making Matano analyses of concentration-penetration curves. However, the accelerating increase in B, which they demonstrated as the phase boundary composition is approached at constant temperature and the rapidly diminishing accuracy of this analysis as the limiting compositions of a diffusion couple are approached (the silicon-rich component of their couples contained appreciably less silicon than is permitted by the solubility limit) indicate that the required information cannot be safely obtained by extrapolation of their data. Although the quite different method employed in this study is not exact, it will be shown that the approximations made are not serious ones, particularly from the viewpoint of the prgcipal application anticipated for these data. D, was determined from the migration kinetics of the a :k boundaries formed in sandwich-type diffusion couples produced by welding a block of high-purity copper to opposite sides of a cube (* in. on edge) of homogenized high-purity Cu-5.82 wt pct Si alloy. The alloy is pure k in the temperature range employed. The surfaces of the couple components which were normal to the diffusion direction were machined accurately flat and parallel, lightly polished, and carefully cleaned. Welding was then accomplished by means of the vacuum-encapsulated pressure jig technique previously employed.3 Welding was always conducted at the intended diffusion temperature; thus the welding anneal also served as the first diffusion anneal. Subsequent diffusion anneals were performed in evacuated Vycor capsules. Following the welding anneal, one of the surfaces parallel to the diffusion direction was machined, ground, and polished flat; additional material was removed from this surface after each diffusion anneal in order to avoid any effects of composition changes. After etching,4 the average distance between a : k boundaries was measured by means of a traveling microscope with an accuracy (per measurement) of better than 1 p. Satisfactory results were obtained at four temperatures in the range 775° to 655°C; attempts to obtain data at two lower temperatures were unsuccessful, evidently as the result of the interference of surface contamination during the welding process.

Jan 1, 1969

By Fritz Wald, Richard W. Stormont

lHE general constitution of a number of metal-lead telluride and metal-tin telluride systems has recently been studied in an effort designed to furnish background information for the study of degradation mechanisms on junctions between thermoelectric power generation materials and metals.1"4 This paper reports further results of that effort. It was found that cobalt-lead telluride constitutes a stable pseudobinary section through the ternary Co-Pb-Te system. Materials used in the study were lead and tellurium of semiconductor-grade purity (American Smelting and Refining Corp., 99.999+ pet). Cobalt (Johnson Matthey & Co., 99.999 pet purity) was used in the form of slices cut from rods of 5 mm diam. Twenty- gram charges of the alloys were melted in evacuated quartz ampoules. Thermal analysis, as described previously,2'3 and metallographic and X-ray diffraction methods (Debye-Scherrer photographs) were used as investigative tools. Substantial difficulties were encountered in polishing, as reported previously for the lead telluride-iron system.3 A number of different etches were used, including dilute aqua regia, Murakami solution, an etch containing copper nitrate,3 and HC1-HNO3-acetic acid-water mixtures. None of these etches gave consistent results over the complete range of cobalt concentrations. On the alloys containing bulk cobalt in the form of primary

Jan 1, 1969

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By H. J. Engell, W. Frank, A. Seeger

SWISHER and ~urkdogan' have determined the solubility of oxygen in a iron. They found it to lie between 7 and 10.5 at.-ppm at 881°C. Using earlier work on the permeability of oxygen in bcc iron,' they arrived at the following expression for the diffusion coefficient of oxygen in bcc iron (k = Boltzmann's constant, T = absolute temperature): where The present authors3 have estimated the activation energy QD for the diffusion of oxygen in bcc iron in two different ways from various experimental data.2'4"6 In the first method QD + QS (QS = heat of solution for oxygen in bcc iron in thermodynamic equilibrium with solid FeO) was determined either from data on the reduction of FeO with hydrogen4 or from measurements of the internal oxidation of silicon in a iron.5 Using an estimate of QS from investigations of the oxygen solubility in 6 iron2 (in thermodynamic equilibrium with molten FeO) Q = 0.97 ev or Q~ = 1.06 ev were obtained. From the magnitude of these values it was concluded that oxygen migrates interstitially in bcc iron and that consequently the activation energy QD for diffusion of oxygen has to be identified with the migration energy E~ of the oxygen atoms. Therefore, for a second estimate of QD from the diffusion coefficient of oxygen in 6 iron at 1450" ~,~ we used the theoretical expression:3 (a = length of elementary cube edge, m = mass of interstitially diffusing atom, sM = migration entropy), applicable to diffusion via the octahedral interstices in bcc lattices. Taking sM = 3.8 k (migration entropy of carbon in a iron), one gets Q = 0.90 ev. Hence, in Ref. 3 Q = (0.98 *0.1) ev was proposed as a plausible value for the diffusion energy of oxygen in bcc iron. sM + 9 (9 = solution entropy for oxygen in bcc iron) can be determined from permeability measurements.4 Using the above-mentioned estimate for QS , the following expression for the solubility c (atomic concentration) of oxygen (in thermodynamic equilibrium with solid FeO) in bcc iron was derived: From [4] the solubility of oxygen at 881°C in a iron is calculated to lie between 0.6 and 12 at.-ppm. We see that the solubility determined by Swisher and

Jan 1, 1969

By J. H. Bechtold, R. Kossowsky

1 HE superplastic behavior of the eutectoid A1-78 wt pct Zn alloy has been thoroughly investigated by Back-ofen et al.' The superplastic elongations and the marked resistance to necking were rationalized in terms of high strain rate sensitivity. In a subsequent paper2 superplastic behavior was formulated to show Nabarro-Herring diffusional creep as rate controlling at low strain rates, giving way to a dislocation climb process at higher strain rates. In a paper devoted to an interpretation of superplasticity in two-phase alloys, Packer and sherby3 have included the results of an examination of the structure of an Al-Zn eutectoid specimen before and after superplastic deformation. No significant change in grain size or directionality was observed in the deformed microstructures. This one observation led the authors3 to suggest that con- tinuous recrystallization or grain boundary migration was responsible for superplasticity. The purpose of this note is to report our observations on the superplastic behavior of the Al-Zn eutectoid alloy which differ in certain respects from works previously reported. Following Hayden et al., the results are discussed in terms of dislocation climb as the important factor during superplastic deformation. A heat of nominally high (99.995) purity 22 wt pct A1-78 wt pct Zn was induction-melted and cast into a 0.5 by 6 by 12 in. slab. The slab was heated to 350°C and rolled to 1/8-in.-thick plate. The plate was then cold-rolled to 0.040-in. thickness, annealed at 35OaC, and rolled to the final thickness of 0.020 in.* Speci-

Jan 1, 1969

By A. U. Seybolt

DURING the course of an investigation of hot corrosion of nickel-base superalloys (combination oxidation-sulfidation attack at high temperature), it was considered possible that sulfur might gain entrance to the alloy in part, at least, by diffusion through the scale. Cr203 is nearly always observed as a prominent component of the oxide scale, and hence some experiments were carried out to examine the tracer diffusion of sulfur through Cr203 at 1000° C in the upper temperature range experienced by jet engine blades and vanes. Some hot-pressed Cr203 discs of quite high density were available from an earlier investigation1 on the rate of crf3 migration through Cr203. The Cr203 was 99.3 pct pure and contained -0.06 pct Fe as the largest metallic impurity. Additional data is given in Ref. 1. In this earlier work it was found that the rate of cation diffusion was independent of the atmosphere of thermal equilibration when using nitrogen, argon, or air, and also that the electrical conductivity of the hot-pressed Cr203 compacts was likewise independent of atmosphere in this range, thus indicating that the de-

Jan 1, 1969

By David L. Holt

It is well-established that hydrostatic pressure distribution is hardly achieved during uniaxial compaction of powders. All the previous investigations1-4 give consistent results and this variation is attributed to the die-wall friction. The conclusions are based on measurements of the density of very small portions of the compact. Although the analysis of the density or the strain distribution in the compact is very helpful in obtaining information about the stress distribution within a powder compact, it does not describe the problem from a more fundamental point of view. The densification in metal powder compacts takes place chiefly by plastic deformation (ignoring particle rearrangement) at the points of contact of the powder particles. The onset of yielding and subsequent growth of the contact areas (for spherical powders) take place fixed by a constant stress equal to three times the yield stress in tension or compression,5-7 assuming little or no work hardening. Therefore, by deforming spherical powders in the die and measuring the contact areas on each particle, the load at each contact point can be determined. In the present investigation, this was done by hot-pressing uniform spheres of lead, K-Monel, and sapphire. The details of the experiment have been described elsewhere.' The spheres were studied for the size and the number of contact points on each particle using a specially designed goniometer. It was found that the deformed faces that were approximately normal to the direction of pressing were about 2.2 times larger than those parallel to the direction of pressing. Fig. 1 shows the typical deformed sphere. A detailed study showed that the mean value of the contact areas on each sphere was within 5 pct for all the spheres in the die (ignoring those touching the die walls and the top and bottom of the die).' The spheres touching the die walls and the top and bottom of the die were found to have larger contact areas (8 to 10 pct) which indicates higher pressures in these regions of the compact and thus higher compact densities in these regions. These results show that density distribution calculated from such an experiment will give results consistent with the previous investigators. It is concluded, therefore, that the pressure distribution in the die is better understood by studying contact areas on each particle. 'R. Kamm, M. A. Steinberg, and J. Wulff: Trans. TMS-AIME, 1947, vol. 171, p. 439. 'Pol Duwez and Leo Zwell: I. Metals, 1949, vol. 1, p. 137. 'G. C. Kucynski and I. Zaplatynskyj: Trans. TMS-AIIME, 1956, vol. 206, p. 215. 'R. P. Seelig and J. Wulff: Trans. TMS-AIME, 1946, vol. 166, p. 492. 'H. Hencky: Z. Angew. Math. Mech., 1923, vol. 3, p. 241. "J. Ishlinsky: I. Appl. Math. Mech. USSR, 1944, vol. 8, p. 233. 'D. Tabor: Proc. Roy. Soc. (London), Ser. A, 1948, vol. 192, p. 247. 'Ashok K. Kakar and A. C. D. Chaklader: 1. Appl. Phys., 1967, vol. 38, p. 3223. Superplasticity in 60Zn-40Al David L. Holt THE occurrence of superplasticity in Al-Zn alloys is of interest because of its possible industrial exploitation.' The eutectoid composition (78Zn-22A1) has been the most extensively studied;'-= neck resistant flow and high strain rate sensitivity of flow stress (characteristic of superplasticity) are associated with a micron-size grain conferred on the alloy by an homo-genization and quench.5'6 Compositions away from the eutectoid have received comparatively little attention, especially from the viewpoint of relating the structural

Jan 1, 1969