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In this Part, we have included copies of the flip charts and overhead projector viewgraphs used in the two briefings we conducted as part of this seismic detection and location task. The first one was an overview and problem definition briefing given to the seismic consultants on September 7, 1972. The second was a formal oral presentation of study results to technical staff members of the Pittsburgh Mining and Safety Research Center on November 21, 1972.

Jan 1, 1974

By G. S. Baker, S. H. Carpenter

Langenecker has reported significant reduction in strength of high-strength metals during ultrasonic t'ibration. Decreases in static yield stress an order of magnitude greater than the calculated stress amplitude of vibrations were reported by him for a stainless steel and for tungsten. in the present work, attempts were nzadc to verify such large reductions in yield and flats stresses using resonant librations of measured amplitudes. The results show that both the soft metals (copper and aluminum) and the high-strength metals (sleels) hare reductions in yield and .flow stresses no larger than the stress amplitude of libration. BLAHA and Langenecker,' investigating the effect of vibratory stresses on the deformation of zinc and aluminum, found a decrease in the static yield and flow stresses approximately equal to the vibratory stress imposed. Langenecker later extending this work to high-strength metals such as stainless steels and tungsten2 found a much larger effect. In these metals the static yield and flow stresses decreased by an amount more than an order of magnitude greater than the calculated vibratory stresses. It was suggested that this phenomenon could be a serious hazard to high-strength structures in an acoustic environment, such as a large rocket at launch, or could be used advantageously in the working of hard-to-work materials such as the refractory metals. Langenecker and others3 have investigated the effect of high-amplitude vibrations on many metal-forming operations. The results have been quite favorable with usually a large decrease in the energy necessary for the forming operation. The processes, however, involve large frictional forces and it is not clear whether the decreases in forming forces are to be ascribed to decreased friction or to decreased flow stresses. The present paper reports an attempt to determine the effect of accurately known vibratory stresses on the static yield and flow stresses. I) EXPERIMENTAL TECHNIQUE The standard multicomponent resonator technique for measuring internal friction has been adapted to allow simultaneous high-amplitude vibration, internal-friction measurement, and tensile deformation. This has been described in detail elsewhere.4 Longitudinal oscillations of approximately 50 kc frequency are excited in a multicomponent resonator by a quartz transducer. A second transducer measures the amplitude of vibrations. Fig. 1 shows a schematic drawing of the resonator and grip arrangement and the displacement pattern produced. Since the centers of the dummy bars are at displacement nodes, they represent points where attachments will not materially affect the vibrations. The force is applied by a standard Instron tester. The sample may be deformed while simultaneously vibrating at up to 104 strain amplitude. 11) EXPERIMENTAL RESULTS The effect of high-amplitude vibrations on the yield and flow stresses of copper. aluminum, tantalum. a soft iron, and a stainless steel has been measured. In addition samples of tungsten vibrating at stress levels up to 10' dynes per sq cm have been subjected to static stresses near the static yield stress with no indication of macroscopic deformation. Fig. 2 gives typical results for 99.999 pct polycrys-talline copper. A vibratory stress of 7 x 107 dynes per sq cm is applied at points "a" and removed at points "h". The behavior of aluminum is identical. In agree-

Jan 1, 1967

By Richard L. Ashbrook, John F. Wallace

Several high-temperature eutectics of cobalt and nickel alloys were modified by small additions of selected elements. Thes-e alloys were compared to unmodified melts for microstructural variations. A few modified compositions were selected on the basis of structure and their tensile and stress-rupture behavior determined. The results of stress-rupture tests in air at 1800 F and room-temperature tensile tests of four high-temperature eutectics showed modification capable of producing substantial improvements in properties. The microstructures were altered and mechanical properties improved by: a.) dispersing a subordinate phase more uniformly throughout the matrix; b) replacing large continuous -network or platelike constituents with small equiaxed discontinuous phases; and c) by forming new, finely divided phases. tHE term "modification" is most commonly used to describe the refinement in microstructure of the Al-Si eutectic that occurs as a result of rapid cooling from the melt or on slow cooling after treatment with small amounts of sodium.1 "Modification" has also been used to describe the change from flake to spheroidal graphite in the austenite-graphite eutectic of cast iron.2 This change of graphite shape is accomplished by small additions of cerium or magnesium.3 Other systems have also been shown to be capable of modification, for example: Pb-Sn by copper;4 Al-Cu by sodium;5 Al-Mn by sodium;5 and Pb-Sb by aluminum.5 Although modification of Al-Si alloys and cast irons is usually accompanied by improved mechanical properties, a general definition of modification has been suggested to include the effect of small quantities of impurity elements on the microstructures of all eutectic alloys, regardless of the effect on the mechanical properties.6 In this paper, the term "modification" is employed in a broad sense to include the formation of third phases or even the supplanting of one of the binary eutectic phases by a third phase. The mechanism of modification, as for any solidification phenomenon, must be considered primarily in terms of nucleation and growth. Although both nuclea-tion and growth mechanisms are required to explain all the phenomena observed in connection with the solidification of modified eutectics, various investigators have usually favored one or the other.7"16 It has been shown that modification of a binary eutectic can be effected by addition of a solute element that has greatly different distribution coefficients or k values in the two phases of the eutectic. Under these conditions, differences in the temperatures at the solid-liquid interfaces of the two phases retard the growth of one phase with respect to the other.4 It has also been shown that increased undercooling favors a transition from a rodlike eutectic to a globular eutectic.17 A mechanism proposed for the transition from lamellar to rodlike eutectics depends on the concept of constitutional super cooling.18 The modification of eutectic alloys may be of interest for high-temperature service as well as at room temperature. Although "high-temperature eutectic alloys" may appear to be a contradiction in terms, many eutectic systems, including those studied in this work, have melting points in excess of 2400°F. One of the mechanisms by which high-temperature alloys are strengthened is dispersion of a relatively brittle phase such as an oxide, carbide, or an inter-metallic compound throughout a ductile matrix. For a given volume fraction of dispersed phase, strength is increased by decreasing the size and spacing of the dispersed particles.19'20 Furthermore, room-temperature ductility may also be increased by changing the shape of a brittle dispersed phase from platelike to equiaxed or spheroidal.8 Overaging and redissolving of the secondary phase limit the maximum temperature to which precipitation-hardened alloys can be used. However, in a binary eutectic system, both phases coexist up to the melting point. Although all eutectic structures are not completely stable,21 a dispersion-hardened cast high-temperature alloy might result if a fine distribution of one of the eutectic phases could be obtained during solidification. An additional reason for interest in eutectic alloys is their excellent castability.22 Since eutectic alloys, like pure metals, freeze at a single temperature rather than over a range of temperatures, their castability is superior to solid-solution alloys with long liquidus to solidus ranges. The purpose of this research was to study the effects of small solute additions on the microstructure and mechanical properties of a number of high-melting-point eutectic compositions.

Jan 1, 1967

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10' cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.' This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.'-= At the same time, the material shows considerable ductility.3'4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin's relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1' presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.'3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella's reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With' elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

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

ELectvon-probe analgsis has been used to in7:estigatr the partition ot alloying- elements between aus-tenite and proeutectoid ferrite (or the Jerritic component of bainite) in high-purity Fe-C-X alloys, lsuully at tzco levels of carbon content fca 0.1 and 0.4 pct in ntost steels) at temperatures between the M, and the Ae3 in Si, mn, Ni, mo, Co, Al, Cr, Cu, and PI steels. No partition ous found during the early stages of transformation at any temperature studied in the Si, ,mo. Co, Al, Cr, and Cu steels. Partition did take place, Jrowel'er, in Ihe Mn, ATi, and Pt steels, occurring in lewtperature. regions below the Ae3 of ca 130°, 65", UNDERSTANDING the mechanisms through which alloying elements influence the kinetics of austenite decomposition reactions which proceed by nucleation and 35c respectively. A break was discovered in the TTT curve for the initiation oj the proeutectoid ferrite reaction in the latter steels at the temperature at which partition began. The alloy content in ferrite at the a:y bondavy remained at constart lecels, shown experimentally to be significantly above those corresponding to eqiilib+iu??l, e'en at the longest reaction times investigated (ca 1o6sec). The partition and the TTT curve observations foere rationalized on the basis of the thermodynamic treatment developed in an accompany ing paper. and diffusional growth has been a major research objective of physical metallurgy since the latter part of the 19th century. The measurements made on the dif-fusivities of carbon and of substitutional alloying elements in austenite during the 1930's and 1940's seemed to provide a useful clue as to the nature of these mechanisms. These measurements showed that the diffu-sivity of carbon is several orders of magnitude higher than that of the alloying elements at a given tempera-

Jan 1, 1967

By S. R. Goodman, Hsun Hu

The formation of secondary - recrystallization tex-tlires in cube-textured 18-8 stain less steel (Type 304) Ilas been studied at three temperatures. Prolonged annealing at 100°'C protluces a PredoninanGly (520) [OOZJ-type texture, which is related to the cube te.ture of the primary lnatrix by a rotation of approxivzately 22 deg around the [001] axis in the rolling direction. Annealing at 1200 or 1300°C facers the formation of the (123)[272/-type texture, which is related to the matrix texture by a [111] rotation of app.voxiniately 40 deg. These observations suggest that in the secondary recrystallization of cube-texlut-ed stainless steel an apparent actilation energy for growth is higher for grains related to the tncrtuix Og [111] rotations thun those reloted by [100] rotations. THE formation of secondary-recrystallization textures in cube-textured primary matrices of fcc metals has been studied widely by various investigators. For Fe-40 pct Ni alloys, Pawlek' and wassermann2 reported that the orientations of secondary grains were related to the cube texture by rotations of 30 and 38 deg around [001] in the rolling direction. However, Rathenau and custers3 found that, while in one Fe-48 pct Ni alloy, most of the secondary grains were oriented with respect to the cube-textured matrix by rotations around [001] of 26.5 deg, in another alloy of a different origin, the orientations of secondary grains were related to the cube texture by rotations of approximately 35 deg around a [lll] axis. Similar orientation relationships were also observed between the secondary grains and the cube-textured primary matrices of copper.4"a No attempt was made to differentiate these two types of orientation relationships; reorientation by either a [111] or a [100] rotation was considered to be equally favored. The present investigation consisted of a study of the secondary recrystallization textures in cube-textured stainless steel. It was noted that the secondary grains formed in stainless steel were considerably smaller than those of Fe-Ni alloys or copper. This offered the advantage that the secondary recrystallization texture could be determined by the texture-goniometer technique, and a more detailed study of the textural development during the course of secondary recrystallization could be made. The effect of annealing temperature on the formation of secondary-recrystallization textures was also investigated. MATERLAL AND METHOD It was shown earlier"-" that a strong cube texture can be obtained in 18-8 stainless steels by rolling at 800°C to produce the copper-type deformation texture, followed by annealing at 800" to 1000°C for recrystallization. To improve the cube texture for the present study, a commercial-grade 18-8 stainless steel (Type 304) was rolled at 800°C first to 5 mm (0.2 in.) thick plates. Three of these plates were then stacked and welded together along the edges into a sandwich assembly. After annealing at 900°C for 20 min: the assembly was finally rolled at 800'C to 90 pct reduction in thickness with reheats and end-for-end reversals after each pass. Only the central strip, which was reduced from 5.0 to 0.50 mm (0.7 in. to 0.020 in.) thick, was used. The chemical composition of the steel in weight percent was as follows: C, 0.06; Mn, 0.38: Cr, 18.71; Ni, 9.56: P, 0.011; S, 0.009; and Si, 0.39. The purpose of rolling the strip in a sandwich assembly was to prevent direct contact between the central strip and the rolls. It was observed earlier" that, when the strip was rolled at 800°C without being enclosed in a sandwich assembly, the cube texture obtained by subsequent annealing at 900" or 1000° C for recrystallization was largely confined to the central section of the strip, while most of the recrystallized grains formed in the surface section of the strip were not cube-textured. This was obviously due to the fact that the actual temperature at the strip surface during rolling, as a result of direct contact between the strip and the cold and massive rolls, was considerably lower than 800°C. By using a sandwich assembly for hot rolling, the cube texture obtained upon subsequent annealing for recrystallization was found to extend through the entire thickness of the strip. After rolling, the central strip was taken from the sandwich assembly. and cut into specimens. Prior to annealing. the specimens were etched to 0.25 mm (0.010 in.) thick. A tube furnace provided with a purified, dry argon atmosphere was used for annealing. Textures were determined by the reflection technique. using a Siemens automatic texture-goniometer and ZrOz-filtered MoKa radiation. With a time constant of 4 sec. the preferred orientation of the secondary grains could be measured satisfactorily by the integrated intensities. Both (111) and (200) reflections were measured, and corresponding pole figures were constructed according to the techniques described previously.10 The agreement between results deduced from these two reflections was excellent. RESULTS AND DISCUSSION Secondary-Recrystallization Texture due to Prolonged Annealing at 1000°C. Fig. 1 shows the primary-recrystallization texture of a specimen annealed at 1000°C for 30 min. A substantial improvement in both sharpness and intensity of the cube texture, owing to the present processing method, can be noted readily by comparing Fig. 1 with similar pole figures shown earlier in Refs. 9 and 11. Secondary recrystallization

Jan 1, 1967

Jan 1, 1967

By C. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-'' or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By K. A. Gschneidner, O. D. McMasters, T. J. O’Keefe

X-ray diffraction, differential thermal, ad rnetallo-graphic methods were used to establish the Dy-Pb Phase diagram. Lead additions lower the 1377°C transformation temperature of dysprosium to 1360°C leading to an inverted peritectic reaction. The 327°C melting point of lead is lowered by dysprosium additions to about 326°C yielding a eutectic reaction. A second eutectic reaction occurs at 13.3 at. pct Pb and 1200°C. The dysprosium-richest intermetallic compound DysPb3 melts congruently at 1695°C and crystallizes in the hexagonal Mn5Si3 (D8,) type structure. The peritectic decomposition temperatures for the remaining compounds are Dy5Pb, at 1555C, DyPb2 at 955C, and DyPb3 at 880°C. A fifth compound near the DyPb stoichiometry exists over a 310°C temperature range decomposing at 1130°C by means of an inverted peritectic reaction and melting incongruently at 1440°C. The crystal structures of the compounds are discussed. A systematic study of the rare earth-lead alloy systems is underway in an effort to supply information concerning the alloying behavior of the rare earth metals. The Dy-Pb phase diagram is the fourth system to be investigated in this study. The Yb-Pb,1 Y-Pb,2 and Eu-Pb 3 diagrams have been published recently. Utilization of the rare earth series of metals as a research tool in this manner should yield a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The lead used in this investigation was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The dysprosium was prepared in this Laboratory by the calcium reduction of the fluoride followed by distillation of the dysprosium. The major impurities in the dysprosium in ppm are: A1 (<40), Ca (400), Er (<50), Gd (<200), Ho (<200), Mg (<50), Si (30), Ta (400), Tb (<100), Y (<50), 0 (651, H (15), N (not detected), F (430), C (35). Alloy Preparation. Most of the alloys were prepared by melting weighed amounts of dysprosium and lead in sealed tantalum crucibles. The tantalum crucibles were sealed by are-welding in a He-Ar atmosphere welding chamber. Thus the alloys are in contact with He-Ar at about 1 atm pressure. Homogenization was achieved by holding them in the liquid state for about 1 hr, cooling, inverting the crucibles, remelting, and repeating the process at least twice. Since these alloys were prepared in sealed tantalum crucibles, chemical analysis for final composition was thought to be unnecessary. No detectable reaction of these alloys with the tantalum crucible was observed by metallographic examination. Metallographic evidence was also used to confirm the homogeneity of some of the alloys prepared in this manner. The compositions of a few alloys, which were prepared by nonconsum-able are-melting, were corrected for the small weight losses involved by assuming that the weight loss is due to vaporization of lead. The specimens obtained from the alloy samples were prepared under a dry-argon atmosphere because they were rapidly attacked by air and moisture. Thermal Analysis. Differential thermal analysis methods were used to determine the liquidus curves and reaction horizontals of the system. Both Pt vs Pt + 13 pct Rh and W + 5 pct Re vs W + 26 pct Re thermocouples were used to measure the temperature. An X- Y recorder was used to record the specimen temperature and differential electromotive force between the specimen and molybdenum standard. The arrest temperatures were measured potentiometri-cally. The accuracy limits (* values) associated with the reaction temperatures obtained by this method were estimated on the basis of both the reproducibility of the particular temperature value and the accuracy of the thermocouple at a given temperature. Liquidus temperatures were obtained from cooling arrest data while both heating and cooling arrest data were used to establish the horizontals of the diagram. Heat treatments during the thermal analyses of the alloys between 40 and 70 at. pct Pb were necessary in order to approach equilibrium conditions. The samples were held at temperatures between the various peritectic horizontals for l to 2 hr before the thermal analyses were continued. The entire range of compositions was investigated at the expense of a minimum amount of materials by adding appropriate amounts of lead to master alloys. More than sixty alloys were analyzed by this differential thermal method and for each alloy the results given herein are taken from two or three heating and cooling cycles. X-Ray and Metallographic Methods. Slice specimens for metallography and powder specimens for X-ray diffraction were prepared from rod-shaped samples which had been melted in sealed 0.62 5-cm-diam tantalum crucibles. The specimens were heat-treated in sealed tantalum crucibles which were protected by sealing them in argon-filled quartz ampules. Quenching was accomplished by breaking the ampules in ice water after heat treatment. X-ray powder specimens were sealed in 0.3-mm-diam glass capillaries under a dry-argon atmosphere. Copper, iron, and chromium radiation were used to obtain the powder patterns for these alloys. More than 150 powder patterns were obtained for specimens of various compositions and heat treatments. Included in these were several patterns for specimens which had purposely been oxidized. Patterns from specimens which had been accidentally exposed

Jan 1, 1969

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.&apos; Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.&apos; For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By Owen F. Devereux

Two discrete types of microstructure me seen in cermets formed by the reaction: 4Al (liquid) + 3SiO2 (glass) — 2A12O3(a) + 3Si (solid) Relatively coarse-grained macroscopically isotropic specimens resulted from reaction with aluminum containing appreciable silicon, while macroscopically anisotropic fine-grained specimens were formed by reaction with aluminum low in silicon. Optical microscopy, electron microscopy, and X-ray diffraction suggest that the anisotropic material contains gross areas in which submicroscopic grains of a A12O3 are oriented along radial lines drawn from the specimen surface. These lines are presumed to originate at defects in an otherwise protecting surface layer. A unique cermet is formed by the reduction of high-silica glass by molten aluminum according to the reaction: 4A1 (liquid) + 3SiO2 (glass) — 2A12O3 (a) + 3Si (solid) The free-energy change accompanying this reaction is -150 kcal at 800°C; the volume change (volume of A12O3 and silicon minus volume of SiO2) is +6 pct. The reaction product, however, contains aluminum metal as well as Al2O3 and silicon because some of the product silicon is dissolved in the aluminum bath and is replaced by aluminum in the structure. The product is a hard gray solid that retains the external dimensions of the original silica article. The system has been studied in the past, the investigations culminating in patents to George1, 2 and Saw-chuk., The former emphasize that this reaction is but one of a relatively broad class of such systems, while the latter demonstrates that a marked improvement in the gross physical properties of the cermet can be obtained by dissolving appreciable quantities of silicon in the aluminum reactant. The system has also been studied by workers at Rolls Royce Ltd.,4-6 who have patented the addition of small quantities of arsenic, antimony, bismuth, or phosphorus to the reactant bath to SO impede the reaction that glass fibers may be metal-coated by immersion in molten aluminum.

Jan 1, 1969

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of&apos; copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C&apos;. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.&apos; As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."&apos;- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

By R. K. Govila, E. H. Parkison

THE interplanar angles for hcp metals vary with c/a ratio, and therefore must be computed separately for each particular metal or alloy. Manual computation of these angles is laborious and time consuming, and for this reason computer programs have been developed to accomplish this task.1"3 However, these programs have certain disadvantages. For example, they require prior knowledge and understanding of ALGOL or FORTRAN languages. Further, they will not print out specific angles but instead give all angles between given limits—thus program2 prints out a total of 26,649 angles between planes with indices and in the range from (4 4 4) to (4 4 4) for any given c/a ratio. The purpose of this note is to present a simple and inexpensive computer program for accomplishing this task. This program is written in BASIC language4 which does not require any prior knowledge of computer programming, and is ideally suited for nonprofessional programmers. It also provides flexibility for the user by allowing him to select any indices for as many or few planes as desired for any given c/a ratio. The computer program proposed below is based on the relationship in which + is the angle between any two planes and . TO illustrate use of the program, consider the problem of calculating the interplanar an-

Jan 1, 1970

By Ashok K. Sinha

The quasi-binary systems "VFe3"—VCo,—VNi,— "VCu3"and "TiFe3"—TiCo3,—TiNi3-"TiCu3"have been studied by a combination of microscopic and X-ray methods. Of the Phases encountered, eleven had close-packed ordered layer structures. Within each system, there is an approximately linear variation of the degree of hexagonality of the stacking arrangement with electron concentration, e/a. A study of eighty -four known examples of AB3 structures in transition metal alloys indicates that at e/a = 8.65 the ordered structure of the close -packed layers changes from "triangular" (AuCu3 type) to "rectangular" (SbCu3 type). At e/a < 8.65, the slope of hexagonality us e/a line increases with the group number of the A component. An interesting series of close-packed ordered structures is known to exist at the composition AB3; however, their alloy chemistry has not yet been fully understood. Dwight and Beck1 observed a correlation between position of the components in the periodic table and the type of crystal structure of the binary AB2 structures formed by transition metals. No consistent effect due to atomic size was noted and they proposed that electron concentration* predominates in In the present paper, the AB3 structures are characterized by a symbol describing the stacking and a symbol specifying the ordered layer. The stacking symbol used was introduced by Zhdanov,7 and later used in the International Tables,8 and by Beck9 in his survey of possible layer stacking structures. Alternating positive and negative integers are used to represent the number of positive (e.g., in abcabc...) and negative (e.g., in cbacba...) stacking sequences. T denotes the triangular ordering found in close-packed planes of the AuCu3 structure and R the rectangular ordering found in close-packed planes of the SbCu3 structure, Figs. 3(a) and (b). The present structure symbols are listed in Table I alongside the prototypes, where known, and other structural characteristics of AB3 phases found in the present investigation. EXPERIMENTAL The starting materials were metals of 99.9+ purity. The alloys were prepared by arc melting under argon atmosphere using a nonconsumable tungsten electrode and water-cooled copper hearth. The total weight loss upon melting and subsequent annealing was always less than 0.5 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. The alloys were homogenized and annealed at suitable temperatures in the range 750" to 1200°C, the annealing periods varying from 3 days at 1200°C to 10 days at 750°C. The heat treatments were carried out in sealed silica capsules under argon atmosphere and with a molybdenum foil cover between the alloy and the walls of the capsule. The quenched alloys were microscopically examined and reduced to powder by crushing or filing. The powders were, whenever necessary, given a stress-relieving anneal at the original annealing temperature. X-ray powder patterns were obtained with an asymmetrical focusing camera, a Guinier-deWolff focusing camera, or a Debye-Scherrer camera. Cr, Co, or Cu radiations were used. In some cases, to ensure the minimum degree of contamination, the deeply etched specimens were mounted in the asymmetrical focusing camera to obtain an X-ray pattern. Internal silicon standards were employed for lattice parameter determinations. The intensity calculations were made by using a Fortran IV program

Jan 1, 1970