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By G. Y. Chin, W. F. Hosford

It has long been recognized that, for a crystal to undergo an arbitrary shape change by crystallographic shear, at least five independent shear systems must be activated. Taylor1 analyzed the deformation of fcc crystals by {111}<110> slip and showed that the principle of minimum work could be used to determine which combination of slip systems might act to produce a given shape change. Later Bishop and Hi112 attacked the same problem by first identifying the state of stress which could physically activate five or more {111)(110) systems simultaneously and then invoking the principle of maximum virtual work to determine which combination would act for a given shape change. Taylor&apos;s general approach has been used to calculate the active slip systems and the relative strengths during axisymmetric flow of cubic crystals with other deformation modes, including {112}<111> slip3 and {111}<112> twinning.&apos; It is the purpose of this note to identify the stress states capable of activating simultaneously five or more of these systems. {111}<112> Twinning. The {111}<112> systems are defined in Table I and illustrated in Fig. 1. The sense of the shears are those for twinning in fcc crystals. The shear stress on any system may be written in terms of the stress components expressed relative to the 1,2,3 cube axes. For example, the stress For five or more of the systems ij to be activated simultaneously, it is necessary that Tij/T be equal to unity in at least five of the expressions [3], while Tij < T for the remainder. (These restrictions assume that the same shear stress T is required to activate each system and that the shear stress on any system cannot exceed that for its activation.) The discrete values of the stress components A through H which can satisfy these restrictions are listed in Table II together with the values of Tij/T for all systems. It may be noted that Tij/ T is not necessarily zero on all nonactive systems as found by Bishop and Hill for <110> {111} slip. In fact, for the case of twinning Tij/T may reach negative values as large as -2 for shear stress in the reverse direction, Table 11. This means that, if those stress states are to be valid, the shear stress to activate reverse twinning must be greater than twice that for forward twinning. Such stress states are probably valid in view of the directionality of the twinning process. There has been no documentation of reverse twinning thus far. It may be noted that the stress states fall into four classes, which may simultaneously activate eight, six, six, and five twin systems respectively. These solutions may be applied to the {112}(111)

Jan 1, 1970

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.&apos; The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.&apos; There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.&apos; The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2&apos;3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,&apos; and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By C. Atkinson

A method is described for the numerical solution of the diffusion equation with a composition-dependent diffusion coefficient and applied to the radial growth of a cylinder; the radial growth of a sphere, and the symmetric growth of an ellipsoid. Sample applications of the method are made to the growth of particles of proeutectoid ferrite into austenite. RECENTLY&apos; we described a method for numerical solution of the diffusion equation with a composition-dependent diffusion coefficient for the case of the growth of a planar interface. In this paper we extend this method to describe the radial growth of a cylinder, the radial growth of a sphere, and the symmetric growth of an ellipsoid. In the latter case, limiting values of the axial ratios of the ellipsoid reduces the problem to one of a cylinder, a sphere, or a plane depending on the axial ratio. A check on these limiting values is made in the results section. In all of these cases we consider growth from zero size. A natural consequence of this assumption as applied to the sphere, for example, is that the radius of the sphere is proportional to the square root of the time. This is consistent with the condition that the radius is zero initially, i.e., grows from zero size. It may be argued that it is more realistic to consider particles which grow from a nucleus of finite initial size; even in this case the analysis of this paper is likely to be applicable. This can be seen if a comparison is made of the work of Cable and Evans,2 who consider a sphere of initially finite size growing by diffusion in a matrix with a constant diffusion coefficient, with the results of Scriven3 for growth from zero size. This comparison shows that the rates of growth in each case differ trivially by the time the particle has grown to about five times its initial size." This investigation is a generalization of those of Zener,4 Ham,5 and Horvay and cahn6 to the situation often encountered experimentally, in which the diffusion coefficient varies with concentration. First let us consider each of the cases separately. I) GROWTH OF SPHERICAL PARTICLES FROM ZERO SIZE In this case the differential equation in the matrix depends only on R, the radius in spherical coordinates, and can be written: ? 1 <^\ ^13D . , dt U\dRz + R 3Rj + dR dR [ J where C is the composition, t is the time, and D is the diffusion coefficient which depends on c. The boundary conditions will be: c = c, at the moving interface in the matrix, c = c, at infinity in the matrix (and at t = 0, everywhere in the matrix), c = X, is the composition in the spherical particle. Each of the above compositions is assumed constant. In addition there is the flu condition at the moving interface which can be written: , dR0 ~/3c dt \dR/H =Ra where R,, which is a function of t, is the position of the moving interface. We make the substitution q = RI~ in [I] reducing this equation to: & - m - *ws) »i where we have written D = D,F(c) or simply D,F, and Do = D(c,). Thus F[c(q0)] = 1 where q, = ~,/a is the value of the dimensionless parameter q evaluated at the interface. Multiplying Eq. [2] by dq/dc and integrating, we find: where the lower limit of the integral has been chosen so that dc/dq — 0 as c — c,, thereby satisfying the boundary condition at infinity. We require, then, to solve Eq. [3] subject to the condition c = c, when q = q, (this follows from putting R = R, at the interface) together with the flux condition which can be rewritten in terms of q as: Eqs. [3] and [4] together with the condition c = c, at q = q0 enable us to find 77, and the concentration profile c = c(q). Numerical Method. We treat Eq. [3] in the same way as we did the corresponding equation for the planar interface problem&apos; i.e., by dividing the interval c, to c, into n equal steps so that: cr = ca -rbc [5] where r takes the values 0, 1, ... n and we call no,, q1, ... nn the values of n corresponding to the compositions c,, c,, ... c,.

Jan 1, 1970

By S. A. Levy, J. D. Wood, J. F. Libsch

A study of the preparation and characteristics of a sevies of Fe-C-N alloys has been conducted. X-ray, microhardness, and metallographic data from a series of single-phase alloys produced by controlled nitriding of carburized foils are reported. The existence of a, y&apos;, and E carbonitride has been confirmed and it has been found that y&apos; is the hardest of these three phases. These results have been used to interpret the structures observed in nitrided steels. ThIS paper represents the second phase of a three-part study concerning combined nitriding and induction hardening. The first part&apos; reports the engineering properties (depth hardness, fatigue, corrosion, and tempering resistance) obtained when seven different steels were subjected to the combined surface hardening treatment. The present paper concerns the nature of a series of single-phase alloys prepared by controlled nitriding of carburized foils. The objective was to simulate the various layers present in the as-nitrided steels. A third paper will report data concerning induction hardening of the foils and will attempt to set forth a mechanism for the high hardness obtained with the combined treatment. Studies of nitriding generally fall into three categories. The first were performed with bars using conventional nitriding procedures, thus yielding a nitrogen gradient and a series of phase layers near the surface.2-6 Such studies were complicated by the presence of the nitrogen gradient, for it was difficult to correlate microhardness and X-ray data with chemical composition. There were always complications due to penetration of the X-ray beam which yielded data influenced by underlying layers. Similar difficulty was experienced in taking hardness readings on a tapered specimen or in isolating various layers by machining. A second group of investigations was primarily concerned with establishment of regions in the Fe-N7,9,10 or the Fe-C-N phase diagram.8 These were performed with powder specimens which were nitrided in am-monia-hydrogen mixtures to produce a series of single-phase specimens. Unfortunately, the powder specimens were not amenable to either microstruc-ture or microhardness study. The third was essentially a compromise of the first two. Bose and Hawkes," using 0.005-in.-thick iron foils, were able to obtain microhardness, microstruc-ture, composition, and X-ray data on Fe-N alloys of eutectoid composition by equilibration in ammonia-hydrogen mixtures at 1290°F. To obtain a better understanding of the nitriding process and the characteristics of the phases in ni-trided plain carbon steels, the present investigation was undertaken. The investigation was patterned after that of Bose and Hawkes with the exception that nitriding was performed at 930°F (below the eutectoid temperature), as in the case of conventional nitriding. In addition to gaining some understanding of the source of high hardness of nitrided and induction-hardened steels, found in a previous study,&apos; this investigation was concerned with the possibility of controlling the phases present in a nitrided case through the use of ammonia-hydrogen mixtures. Knowledge of the properties of each phase and the conditions necessary for its production could make it possible to avoid undesirable surface layers in nitriding. EXPERIMENTAL PROCEDURE Specimen Preparation. A specimen thickness of 0.005 in. was selected to insure that a uniform nitrogen concentration could be obtained in a reasonable length of time by equilibration in an ammonia-hydro-gen atmosphere. The starting material was a vacuum-cast ingot of pure iron, the major impurities of which were: C, 0.003 pct; 0, 0.014 pct; S, 0.004 pct; N, 0.003 pct.* &apos;Compositions are quoted as weight percent except as noted. The ingot was heated to 1500°F in a nitrogen atmosphere and forged to a slab 0.25 in. thick. The material was then reduced to 0.005 in. by alternately cold rolling and annealing in a nitrogen atmosphere at 1600°F. This material was divided into five groups of specimens which, after carburizing, yielded the following carbon contents: 0.003, 0.28, 0.36, 0.46, and 0.74 pct C. The carburizing was performed by the Leeds and Northrup Research Laboratories, using a controlled "carburizing potential" which yielded a uniform carbon concentration throughout the cross section.

Jan 1, 1970

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000&apos; and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,&apos; who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7&apos;&apos; became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9&apos;10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal&apos;guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1&apos;-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77&apos; zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,&apos; silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.&apos; Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2&apos;9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,&apos; grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4&apos;5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.&apos; One aspect of these effects is based on Rehbinder&apos;s theory of crack propagation in materials under stress.9 According to Reh-binder&apos;s theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.&apos;-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

c axis compression behavior of beryllium single crystals at three purity levels under hydrostatic pressures up to 27 kbars was determined. Extensive non-basal slip, observed by two-surface trace analysis and transmission electron microscopy, occurred under a hydrostatic pressure of about 12 kbars (175 ksi) for the high-purity (twelve-zone pass) material and at about 19 kbar (275 ksi) for the lower-purity (zone-leveled) material. Prismatic loops with a (c + a) Burgers vector were observed in association with second-phase parti- A principal factor limiting the use of beryllium is its brittle behavior when tested at the usual strain rates (E = 10-4 sec- 1) at temperatures below about 200°C and under impact conditions at temperatures in excess of 200°C. It has been proposed&apos; that the brittle-ness of beryllium is associated with the lack of a sufficient number of independent slip modes and the absence of a slip mode with a Burgers vector out of the basal plane [presumably (c + a) pyramidal slip mode] and to the ease with which beryllium cleaves on the basal and second-order prism planes. The absence of pyramidal slip has been attributed to a high Peierls-Nabarro stress associated with the motion of dislocations with a (c + a) vector and the ease with which cleavage occurs on the basal and second-order prism planes. The experimental evidence in support of the proposed explanation for the brittleness of beryllium is far from complete; for example, that the ductile-to-brittle transition in polycrystalline beryllium is associated with the operation of profuse (C + a) slip has not been unequivocally established. The occurrence of (c + a) slip ({1122}(1123)) has been experimentally established2-5 under conditions where basal and prism cleavage are restricted in a c axis compression test. In these investigations (C +a) slip was found in high-purity beryllium single crystals tested in c axis compression* at 200°C and in Be-4.4 pct Cu and Be-5.2 pct cles in the lower-purity materials tested. The loops were related to surface "extrusions" observed on many of these same specimens. Nonbasal dislocations operating on (1122) planes with a (c + a) Burgers vector were observed. The presence of c and a dislocations together with (c + a) dislocations suggests that the (c + a) dislocations dissociate presumably on unloading or after failure of the test crystals to c and a dislocations. terial, (c + a) slip has only been observed near the the fracture4 surface in room-temperature c axis compression tests. Fracture in these tests occurs without measurable plastic flow, as determined with a strain sensitivity of 10"6. Since it has been shown for many metals that the application of hydrostatic pressure suppresses fracture,?-&apos; it was felt that studying the behavior of unalloyed beryllium single crystals stressed in c axis compression under a hydrostatic pressure would reveal whether (c + a) can occur if fracture was prevented, and that it might elucidate the role of (c + a) slip in the ductile to brittle transition. Evidence that (C + a) slip is associated with increased ductility in a high-pressure environment has been found in stress-strain tests on poly crystalline beryllium.10 The present paper describes a study on the influence of a hydrostatic pressure environment on the occurrence of (c + a) slip in beryllium single crystals. Material of two purity levels was tested in c axis compression over the pressure range ambient to about 27.5 kbars.* 1) MATERIAL PREPARATION AND CHARACTERIZATION Two lots of low-purity single-crystal beryllium were used. The first lot was "ingot secondary refined grade" and designated lot A. The second lot (lot B) was produced by a two floating zone pass zone-leveling operation in an argon-filled sealed quartz apparatus on a 1-in.-diam by 12-in.-long bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. The high-purity material (lot C) was made by traversing twelve floating zone passes through a similar bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. In a series of spark cutting and lapping procedures,11 single-. crystal specimens some 0.12 in. sq by 0.30 in. high were made with the sides Parallel to the first- and second-order prism planes and the basal plane within 3&apos; of arc of the top and bottom surfaces of the specimen. Such an accurate orientation is necessary because of the large difference in resolved shear stress

Jan 1, 1970

By R. W. Carpenter, J. C. Ogle

It is possible, by using pack-rolling instead of conventional rolling, to reduce a number of metals to thicknesses of 2µm or less. Such thinfoils are generally made at room temperature without intermediate annealing. In addition, pack-rolled foils fail by developing pinholes at thicknesses near 2µm instead of developing the shear cracks usually observed in cold-rolled ductile metals. This paper presents the results of a general investigation of the deformation substructure and texture developed in copper and iron pack -rolled from 130 to about 2µm thickness. Electron microscopy showed that in both metals a fine (0.2 to 0.5?µ m) deformation subgrain structure formed during pack-rolling; in neither case was this substructure grossly different from substructures formed during conventional rolling. The deformation texture formed in pack-rolled iron was quite similar to usual bcc textures; however, in the case of copper, the cube texture was stable during pack-rolling and the normal copper deformation texture was unstable. It is shown analytically that the constraining pack induced a large hydrostatic pressure in the foils during pack-rolling. The pinhole failure mechanism is attributed to the presence of the large hydrostatic pressure during pack-rolling; this strongly suppressed the growth of shear cracks. The stability of the cube texture in copper is also probably due to the unusuul stress distribution developed during pack-rolling. EXPERIMENTS at several laboratories have shown that very thin foils of the common structural metals and many of the rare earths can be made by "pack-rolling". 1-3 The technique was originally developed to make specimens for nuclear scattering experiments and foils for X-ray filters. It is also useful for making experimental laminar metallic composite bodies and foils thin enough for direct examination by ultra-high voltage electron microscopy without the need for special thinning techniques. Pack-rolling in the present context means a three-layer pack, with the material to be rolled into foil comprising the center layer. The outer two layers, which constrain the foil during reduction, are ordinarily austenitic stainless steel. Typically, a 130 µm (0.005 in.) metal strip can be reduced to a final thickness of 2 µm or less by this process. This is accomplished at room temperature, without intermediate annealing. It has been observed that foils produced by this process do not exhibit at any stage of their reduction the severe work-hardening found in strip rolled by conventional cold-rolling methods. Neither is the failure characteristic the same."&apos; Conventionally cold-rolled ductile metal strip fails by developing shear cracks on planes whose normals nearly bisect the angle between the rolling direction and normal to the rolling plane; these are planes of maximum shear stress. In pack-rolling this mechanism has not been observed; failure occurs by the formation of pinholes on the foil surface (penetrating the foil). If pack-rolling is continued the hole density increases. These differences in behavior imply the existence of appreciably different substructure in pack-rolled foils compared to substructure in conventionally rolled material, or perhaps that the geometry of pack-rolling has an effect on the foil behavior. This paper describes an investigation of deformation substructure and texture in some specimens of pack-rolled copper and iron, and some considerations of the stress distribution in the foils during rolling that result from the geometry of pack-rolling. EXPERIMENTAL DETAILS Three different materials were used for pack-rolling in the present work: soft copper sheet (99.8 pct Cu, 0.03 pct 0, electrolytic tough pitch) and two types of iron, Ferrovac E* and Armco iron. Each was "Crucible Stccl Co. initially in the form of 130 µm annealed strip with grain size ranges of approximately 10 to 40 µm. The initial texture of the copper (determined as noted below) was the normally observed cube type (001)[100]; there was evidence of a small amount of material in the cube-twin orientation reported by Beck and Hu.4 The initial texture of the Ferrovac E was similar to that reported for recrystallized iron by Kurdjumov and sachs,5 who list the principal orientations as {111}<112>, {001}<110> 15degfrom RD and a weak component {112}(110) 15 deg from RD. The starting texture of the Armco iron was not determined. Pack-Rolling Procedure. A four-high mill was used for all specimens. The work roll and backing roll diameters were 1.625 and 5.25 in., respectively. The peripheral roll speed of the work rolls was about 2.5 in. per sec. All foils were initially reduced from 130 to 100 µm by conventional straight rolling and then inserted into a pack, without any intermediate annealing, for further reduction. The pack consisted of an 0.033 in. (838 µm) thick 3 by 6 in. polished sheet of austenitic stainless steel, folded to make a 3 by 3 in. jacket. After folding, the jacket was given a small reduction to close the fold tightly before insertion of the foil. During pack-rolling a constant change in roll spacing was made every third pass. The roll-spacing change corresponded to a 5 pct reduction in thickness for a new pack. This approached a 10 pct reduction when the pack had decreased to about half its original thickness. At this point the deformed pack was discarded and a new one

Jan 1, 1970

By H. S. Wang, Y. P. Gupta

Diffusion of zinc and germanium in liquid silver is measured in the temperature range 975" to 1400°C by use of the capillary-reservoir technique. The ex-perinzental results are discussed in terms of the fluctuation and the "hole" theories of liquid diffusion, assunzing the solute as a point charge equal to the difference in the valences of the solute and solvent atoms. The additional coulombic interaction term due to the excess solute charge is evaluated in terms of the Thomas-Fenni approximation. The theoretical and experimental results agree with both the fluctuation and "hole" theories of liquid diffusion. No perceptible effect on solute diffusion in liquid silver of the size difference between the solute and solvent atoms/ions is apparent. DIFFUSION in liquid silver of electropositive solutes indium, tin, antimony, and homovalent gold has been previously reported by Leak and Swalin1 and Gupta,&apos; respectively. These solutes have nearly the same atomic size but differ principally from one another in excess valence (+2, +3, +4, respectively). The observed differences in the temperature dependence and the rate of solute diffusion were explained in terms of an added coulombic interaction between the solute and the solvent atoms. In the case of diffusion of gold in liquid silver, the data were found to be consistent with an effective valence for gold of -0.85, as proposed by Le Claire.3 Recently, Wang and Gupta4 have reported a study of diffusion of ruthenium, iron, and cobalt in liquid silver. The results of diffusion of these solutes and their temperature dependence were found consistent with the hole theories and the fluctuation theories of liquid diffusion, if ruthenium, iron, and cobalt were diffusing in liquid silver with relative valences -2, -1.3, and -0.5, respectively, instead of -3, -3, and -2 as suggested by the relative position of these elements in the Periodic Table of Elements. Furthermore, the predicted valences for these solutes were observed to be consistent with the sparsely available information on the magnetic properties of some of the dilute alloys of copper and silver with these solutes. In theoretical calculations of solute diffusivity, the solute was assumed as a point excess charge equal to the difference in the valences of the solute and solvent atoms. Both the assumption of a point excess solute charge and the use of the Thomas-Fermi approximation to calculate the potential of a solute charge are less precise for the case of electronegative solutes. Therefore, it was not possible to infer from the data on ruthenium, iron, and cobalt an effect, if any, on solute diffusion of the relative differences in either the Period or the size of the solute and solvent atoms or the solute atoms themselves. A study of the diffusion of Period 4 elements, specifically zinc and germanium was, therefore, undertaken since zinc and germanium, respectively, have relative valences of +1 and +3 in liquid silver and the data obtained on diffusion of these solutes could be compared with the available data on diffusion of Period 5 electropositive solutes, indium, tin, and antimony in liquid silver. From such a comparison, it was hoped to learn something about the effect, if any, of the ion size or the structure of the ion core on impurity diffusion in liquid silver. EXPERIMENT The diffusion of tracer zinc and germanium in liquid silver was studied by the capillary reservoir technique, modified adequately for use at high temperatures. In principle, capillaries containing liquid silver

Jan 1, 1970

By W. G. Davenport, M. Paneni

Experiments in sheets of mercury and water have confirmed that the dynamics of bubble rise are simi-lur in Liquid metal and aqueous systems. RECOGNITION that bubble/metal interactions are important in pyrometallurgical refining processes (e.g., steelmaking, vacuum degassing, deoxidation of copper) has led to a number of investigations into the dynamic behavior of bubbles rising in liquid metals. Terminal velocities of bubbles rising in mercury (20°C)&apos; and silver (1000" to 1050"c)1,2 have been measured. Good agreement between aqueous and liquid metal systems has been obtained. Shapes of air bubbles rising in mercury have been determined experimentally by Davenport, Bradshaw, and Richardsonl who used a system of electric probes to measure maximum horizontal and vertical dimensions, Fig. 5. In the present work the motion and shape of nitrogen bubbles rising in a thin sheet of mercury (i.e., a "two-dimensional" environment) have been studied with the view of confirming dynamic similarity between aqueous and metallic systems. The use of thin sheets of liquid permitted direct visual and photographic comparisons of bubble behavior in clear liquids and in mercury. EXPERIMENTAL METHOD The thin sheets of mercury or water were held in a clear acrylic plastic container, Fig. 1. The sheets of liquid were 80 cm high by 30 cm wide and 0.47 cm thick. Single bubbles were formed by injecting the desired volume of nitrogen into an inverted semicircular cup (stainless steel). The cup was then rotated into the upright position using an external handle thus releasing a single bubble of measured volume. Nitrogen was injected into the cup from a nitrogen cylinder through the external handle and a hollow rotating axle. The volume of a bubble (volume range 0.01 to 10 cu cm) at any instant was obtained by connecting a soap film meter to a small gas space above the liquid. By this technique any change in the volume of a gas bubble in the liquid (i.e., during cup filling or during rise) produces an equivalent displacement from gas space A into the buret B. This displacement is determined by measuring the movement of a horizontal soap film in the buret. Bubble shapes were determined using single-frame photography. Rising velocities were determined by cinephotography with a 1/100-sec stopwatch in the field of view. In both cases dimensions were referenced to a rule attached to the container surface, also in the field of view. Linear dimensions were measured on projections of the single-frame negatives. Rising velocities were calculated from measured heights of rise (10 to 20 cm) and times of rise. The effects of disturbances caused by cup rotation and by bubble release were minimized by photographing bubbles at a point not less than 25 cm above the cup. MATERIALS Mercury: Technical-grade purified: minimum 99 pct Hg; Johnson Matthey and Mallory Limited, Toronto. Nitrogen: Technical-grade purified nitrogen: 99.99 pct Nz, 0.01 pct 02, trace argon; Air Liquide Canada Limitee, Montreal.

Jan 1, 1970

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By Pervez Patel, Martin G. Frohberg, Demetrios Papamantellos

Model experiments were carried out on the mass transfer of iodine between n-hexane and a 4 2 X 10-3 M aqueous sodium hydroxide solution. The influence of mechanical stirring by means of small gas bubbles (ca. 0.01 ml in volume) on mass transfer was examined in independent experiments. The results were described with the help of the penetration theory and in the case of bubble stirring with the help of a mathematical model based on this theory. S LAG-METAL reactions, especially those in steel-making processes, often occur under conditions where gas is evolved in the form of bubbles that break through the slag-metal interface. It is known that stirring by means of bubbles increases the mass transfer coefficient, but there has been very little quantitative work done in this field. Because of the difficulties that attach to experimental work at high temperatures this study was confined to model experiments at room temperature. EXPERIMENTAL APPARATUS The transport of iodine from an n-hexane layer into a weak sodium hydroxide solution was studied a) with stirring by means of bubbles and b) with mechanical stirring. The apparatus for the experiments with bubbles consisted of the cell, two Dreschel bottles filled with hexane in order to saturate the nitrogen flow, one flow meter, and a nitrogen gas cylinder fitted with a fine-regulating valve. Fig. 1 shows the cell consisting of a glass cylinder 33 cm in height with an overall diameter of 7.5 cm embedded in a copper flange. The flange is connected to a Plexiglas plate and to the gas inlet. The Plexiglas plate has holes of 0.2 mm diam bored into it which are spaced 1 cm from each other. For the experiments with mechanical stirring the bottom of the cell was sealed off by a Plexiglas plate. The upper layer was stirred by means of a glass stir-rer and the bottom layer with the help of a magnetic stirrer in a counter rotatory direction. Both stirrer speeds could be varied continuously. EXPERIMENTAL PROCEDURE Iodine dissolves in n-hexane producing a stable violet color thus enabling the iodine concentration in

Jan 1, 1970

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.&apos;-&apos; A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y&apos; effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability&apos;1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y&apos; precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.&apos; Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8&apos; at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y&apos; and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By D. O. Hobson, P. L. Rittenhouse

We have recently found that many lots of Zircaloy-2 and -4 tubing tested in tension deform to cross section shapes that are "polyhedral" rather than circular. The noncircular cross sections seem to result from a circumferential variation in plastic proper -ties and, therefore, in texture. We examined the diffracted X-ray intensity from (OOOl), {1010), {ll20}, and {1011} planes parallel to the tubing surface around the entire circumference. Tubing that deformed to a circular cross section showed <5 pct variation in diffraction intensity around the circumference from any of these planes. Greater intensity variations were found for all the tubing materials that developed non-circular cross sections during deformation. In each instance the number of intensity maxima and minima was consistent with the number of sides of the &apos;polyhedral" cross section. THE effects of crystallographic texture on the mechanical properties of zirconium, zirconium alloys, and other anisotropic hexagonal materials such as titanium and hafnium have been intensively studied. If the natural crystallographic anisotropy of these materials could be controlled by selected fabrication operations, a material could be produced with a texture, or preferred orientation, in which the maximum strength directions are in the stress directions of the structure. The permissible stress levels of the structure could then be increased. Rittenhouse and Pickle-simerl have shown that highly textured Zircaloy-2 plate can vary from 52,000 to 70,000 psi in tensile yield and from 62,700 to 122,000 psi in compressive yield strengths as a function of specimen orientation. Similar texture effects have been observed in Zircaloy tubing, whose mechanical properties differ depending upon whether the tubing has basal poles predominantly radial or tangential and upon the mode of testing. These same texture effects might be troublesome if the texture in the tubing is not uniform around the tube walls. This paper is concerned with the effects of nonuniform texture on the strain behavior of commercial Zircaloy tubing. BACKGROUND Previously, various lots of commercial Zircaloy tubing were tested under selected stress conditions as part of a program to determine the four quadrants of the yield locus. One of the testing procedures was uniaxial tension and it is the influence of texture variations on the tensile deformation behavior of the tubing that is of interest here. The effect of texture on the strain behavior in tubing is very apparent from a uni-axial tensile test.2 This behavior is illustrated schematically in Fig. 1 for three different tubing textures: 1) basal poles predominantly in the radial direction; 2) basal poles predominantly in the tangential direction, and 3) basal poles equally distributed between the radial and tangential directions. In the first example most of the grains are oriented for prism slip to operate to allow axial lengthening and diametral reduction of the tube. Reduction in wall thickness requires {1122} twinning, a more difficult operation than slip.* In the second example, the texture is such that *The singleCrystal analogy will be used quite often in this paper when strong texturesare being discussed. The textured material is assumed to react as if it were a single crystal aligned in the same orientation and under the same stress system as the predominant texture._____________________________________________ prism slip operates to give axial lengthening and wall thinning. Diametral reduction requires twinning and again should be more difficult to accomplish. A specimen with basal poles equally distributed between the radial and tangential directions should exhibit about equal diametral and wall strains.* Table I shows the *Diametral strain is accomplished by a combination of circumferential and longitudinal strains. But, for the purposes of this paper, it will be considered as a strain causing a change in the length of a specified diameter.__________ strain behavior of two lots of tubing with different textures. The first tube has a texture with basal poles equally distributed between the radial and the tangential directions. The ratio of true thickness strain to true diametral strain is almost unity. The second tube has a predominantly radial basal pole texture and it is apparent that most of the total strain has occurred by diameter reduction, just as one would predict. There is over three times as much diametral strain as thickness strain. RESULTS We found that specimens from certain lots of commercially fabricated tubing did not retain round cross sections during uniaxial testing. Instead, the speci-

Jan 1, 1970