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By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0' plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8' plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0' occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?' plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0' plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8', formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0' plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,' no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 ' lattices at the orientations of the 0:0' boundary corresponding to the edges of 0' plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,' an experimental determination of the interfacial structure of the edges of 8' plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20'21 has been fully described in a previous paper.'

Jan 1, 1969

By K. A. Jackson

An analysis of the conditiom fm the dendrite-eutec-tic transition is presented which takes into account a temperature gradient. The composition and temperature in the liquid ahead of a eutectic interface growing at a particular velocity are used to determine whether dendrites can grow faster than the eutectic interface in the liquid which exists ahead of it. If the dendrites grow faster, then a mixed structure with dendrites growing ahead of the eutectic interface is expected. If the dendrites do not grow faster, then only eutectic will be present. The analysis is presented for Sn-Pb system, for which sufficient experimental data to make the analysis are available. The transition from eutectic to dendrites-plus-eutectic derived by this analysis is in good agreement with the recent experimental observations of Mollard and Flemings on Sn-Pb alloys. In alloys which grow with a lamellar eutectic structure, the lamellar structure can be grown over some range of compositions close to the eutectic composition. When the composition is too far from the eutectic composition, dendrites of one or another of the primary phases grow ahead of the eutectic interface, producing a microstructure consisting of "primary phase" interspersed with a lamellar eutectic. Hunt and Jackson' have recently predicted the range of compositions over which the eutectic phase should grow in Sn-Pb alloys, and the composition-growth rate dependence of the transition from eutectic to dendrites-plus-eutectic. This prediction was based on work on organic eutectics. The model on which the prediction was based assumed that there was no temperature gradient in the system, a condition approximately satisfied in the study of organic eutectics2-5 but not in the growth of metallic alloys. Mollard and Flemings6,7 have recently reported experimental results for Sn-Pb alloys in which they have located the transition from eutectic to eutectic-plus-dendritic growth. The experiments were performed using large temperature gradients (65 to 515 deg per cm), so that the assumption of zero gradient on which the predictions of Hunt and Jackson' were based does not apply. It is not surprising therefore that the predictions' were not born out by the experiments.7 In the present work, a modification of the model used by Hunt and Jackson is presented which takes into account the temperature gradient. The modified form of the theory predicts the transition from eutectic to eutectic-plus-dendritic growth in terms of the composition, growth rate, and temperature gradient. Good agreement with the experimental data of Mollard and Flemings7 is obtained. THE HUNT-JACKSON MODEL The model used by Hunt and Jackson' to predict the transition from eutectic to eutectic-plus-dendritic growth was based on the assumption that dendrites grow ahead of a eutectic interface only if they grow faster than the eutectic interface. Analytic expressions for the growth rate of dendrites and the eutectic in Sn-Pb alloys were obtained by fitting experimental data with equations whose form was indicated by theory.

Jan 1, 1969

By R. A. Vandermeer, J. C. Ogle

The preferred crystallographic orientations (texture) developed in randomly oriented, poly crystalline niobium during rolling were studied by means of X-ray diflraction techniques. The evolution of texture at both the surface and center regions of the rolled strip was carefully examined as a function of increasing defamation throughout the range 43 to 99.5 pct reduction in thickness. Certain aspects of the center texture development in niobium are in agreement with the predictions of a theory by Dillamore and Roberts, but others cannot be explained by the theory in its present form. Above 87 pct reduction by rolling, a distinctly different texture appeared in the surface layers which was unlike the center texture. The present results are compared with previous results obtained from other bcc metals and alloys. RANDOMLY oriented, poly crystalline metal aggregates when plastically deformed to a sufficiently large extent develop preferred orientations or textures. In a recent review article, Dillamore and Roberts1 pointed out that the nature of the developed texture may be influenced by a large number of variables. These include both material variables such as crystal structure and composition and treatment variables such as stress system, amount of deformation, deformation temperature, strain rate, prior thermal-mechanical history, and so forth. From a practical point of view, the control of preferred orientation may often be important for the successful fabrication of metals into usable components. During the past few decades many experiments have been devoted to the study of deformation textures. This work, however, has been confined in large part to metals and alloys that have an fcc crystal lattice. By comparison, bcc metals and alloys have received much less attention, and consequently our understanding of preferred orientations in these materials is only shallow. This state of affairs worsens when it is realized that almost all of our present howledge about this class of materials derives from studies on irons and steels.' The bcc refractory metals, which are relative newcomers to the industrial world, have, on the other hand, been given at best only passing glances in the area of texture development. Our understanding of the evolution of preferred orientations in bcc metals can only remain fairly limited until systematic studies of metals and alloys other than the irons and steels have been carried out and the influence of the many variables has been determined. To that end a program was initiated to investigate in detail texture development in niobium. The present paper reports some of the results of this study. Textures were determined at both the center and surface of strips rolled variously to as much as 99.5 pct reduction in thickness at subzero temperatures. Emphasis in this paper is on texture description and on texture evolution during rolling to progressively heavier deformation. EXPERIMENTAL PROCEDURE The niobium was purchased from the Wah Chang Corp. as a 3-in.-diam electron-beam-melted billet. Chemical analysis indicated the impurities to be less than 300 ppm Ta, 40 ppm C, 10 ppm H, 170 ppm 0, and 110 ppm N. All other impurities were below the limits of detection by spectrochemical analysis. This large-grained billet was fabricated into specimen stock so that a fine-grained randomly oriented grain structure resulted. This was accomplished in three deformation steps alternated with recrystalli-zation anneals of 1 hr at 1200°C in a vacuum of low 10"6 Torr range after each deformation step. The first step was to alternately compress the billet 10 to 20 pct in each of three orthogonal directions. The second step was to compress in only two directions 90 deg apart to produce a 2-in.-sq bar. The final step was to roll this bar 50 pct to give a 1-in. by 2-in. cross section. After the final anneal, metallo-graphic examination showed the material to have an average grain size equivalent to ASTM No. 5 at 100 times (i.e., 0.065 in. diam). Specimens cut from the center and edges of this bar gave no indication of detectable preferred orientation when examined by X-ray diffraction. Samples 1.5 in. long, either 0.625 or 0.750 in. wide, and approximately 0.400 in. thick were machined from this fabricated ingot. The surfaces corresponding to the rolling planes were ground so as to be parallel. The samples were chemically polished in a solution of 60 pct nitric acid and 40 pct hydrofluoric acid (48 pct solution) prior to rolling to remove any cold work introduced in the machining operations. Rolling was accomplished with a 2-high hand-operated laboratory rolling mill that had 2.72-in.-diam rolls. Prior to operation, the rolls were polished with 600 grit paper, cleaned with acetone, and then soaked in a container of liquid nitrogen for several hours. The samples were also soaked in liquid nitrogen prior to rolling and were recooled between each pass. While some slight heating of the samples occurred during rolling, this procedure maintained the sample temperature well below 0°C at all times. The samples were rolled unidirectionally, and the rolling plane surfaces were not inverted during any phase of the operation. The draft per pass averaged between 0.010 to 0.012 in. After 96 or 97 pct reduction the draft was reduced to 0.001 to 0.002 in. per pass. Samples were rolled to various reductions in thickness between 43 and 99.5 pct.

Jan 1, 1969

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By Hsun Hu, R. S. Cline

In an earlier publication1 it was shown that a single crystal of Cu-4 wt pct Al cold-rolled in the (110)[112] orientation was stable up to 95 pct reduction, although the orientation spread was considerable larger than in a similarly oriented and cold-rolled copper single crystal. When rolled to 99 pct reduction, the copper crystal retained its initial orientation and a high degree of sharpness of texture, whereas the Cu-4 pct

Jan 1, 1969

By D. F. DeSante, A. S. Tetelman

MICROCRACKS are often introduced into commercial metals during fabrication processes such as swaging, cold rolling, deep drawing, and welding. These microcracks act as strain concentrators and may be capable of causing premature catastrophic failure of a component or weld. The present investigation was undertaken to determine whether high-temperature annealing treatments may be capable of reducing or negating the detrimental effects of such existing microcracks. Internal microcracks, ranging from 0.1 to 0.85 mm in length and averaging 0.23 mm, were introduced into polycrystalline Fe-3 pct Si tensile specimens (0.155 mm grain size) by the cathodic charging of hydrogen.1'2 The typical appearance of such microcracks and their associated strain patterns (made visible by the technique of dislocation etch pitting3) is shown in Fig. 1. The stress fields of the dislocation loops formed during plastic relaxation stabilize the microcracks so that, when the internal hydrogen pressure is removed: the microcracks stay open, rather than disappear as perfectly elastic cracks would be expected to do.' As shown in Fig. 2, such stopped microcracks cause a 36 pct decrease in the macroscopic cleavage fracture strength at -196°C.

Jan 1, 1969

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By N. Standish

By contrast with viscometry and sedimentation, no actual measurements of the applicability of Stokes' law to steelmaking have ever been reported; instead, the proof for and against Stokes' law has been inferred from the frequently observed phenomenon that inclusions collect in the top scum and the bottom of ingots. As such proof is unsatisfactory, continued reference to Stokes' law in steelmaking, even as a model for calculating the terminal velocities of rising inclusions, should be avoided. In fact, all conclusions that have been reached regarding size, density, and viscosity on the flotation of inclusions could be made more rationally without Stokes' law. A worthwhile exception is that of Mitsche1 who in 1934 used Stokes' law to show not only the expected effects of size, density, and viscosity on flotation but also the beneficial effects of i) melting under a slag layer (now Electro Slag Refining); ii) treating melts with synthetic slags (Ref. 2 gives recent applications); iii) bubbling an inert gas through the melt (recent applications in Refs. 3 and 4); and iv) altering the solid/ liquid interface characteristics. At this point, it should again be emphasized that the boundary conditions for which Stokes' law was derived place enormous restrictions on the law but its application, as noted earlier, can yield useful results in some fields under certain conditions and within well-defined limits. When compared with inclusions, which may be solid or liquid, spherical or irregular, dispersed or coagulated, interacting between themselves and the melt, floating in a liquid which is in a state of motion of varying intensity5 and contained in vessels of various shapes and sizes that may change with time as in a solidifying ingot, the conclusion is obvious-Stokes'

Jan 1, 1969

By R. W. Smith, G. W. Delamore, J. A. Spittle

RECENT work by the authors1 has demonstrated that the crystals constituting the equiaxed zone in small ingots originate, on quenching, in the chilled liquid. Whether any partial remelting2 takes place of the den-drites nucleated in the chilled region was not examined. However, the claim3 that this normally occurs, leading to crystal multiplication, has been disputed.4 Thus, for an equiaxed zone to form in the central region of an otherwise columnar ingot, it is necessary to transport crystallites from the chill zone to this region. In view of the work of Uhlmann et al.,5 it was considered desirable to examine the transport process further. Experimental Technique and Results. In the earlier experiments by the authors.1 a stainless-steel crucible 17/8 in. diam, 41/2 in. high, ad containing an alloy of A1-4 wt pct Cu, was quenched from 660°C into a bath of Wood's metal maintained at 100°C. Under these conditions a central zone of equiaxed crystals was obtained. However, if a 2250-G unidirectional magnetic field was applied for 2 sec immediately following the instant of quenching, or subsequently, the equiaxed zone did not appear. Careful thermal analysis showed that the short application of the field had virtually no effect on the thermal conditions of the melt. It thus appeared that the crystallites which were ultimately to grow large enough to form the equiaxed zone existed in the liquid immediately ahead of the interface, occlusion being prevented by the convective fluid flow induced by freezing from the walls of the cylinder. When this relative movement was prevented by the Lorenz forces induced by the application of the magnetic field, the crystallites were caught up in the rapidly advancing dendrite solid-liquid interface. To test this assumption, a small ingot of super-purity aluminum was partially melted and poured into a heated stainless-steel mold which was then immediately quenched into molten Wood's alloy. The resulting structure is shown in Fig. 1, and consists of columnar grains with a central fine-grained zone. Thus the unmelted solid present at the beginning of solidification had been transported ahead of the columnar interface. Discussion. There appears to be little or no information available on the interaction of suspended particles with a metallic solid/liquid interface. However, some information is available for transparent organic sys-

Jan 1, 1969

By J. C. M. Li

A dislocation model is constructed for a cylindrical tilt boundary of which the axis of tilt is parallel to the axis of the cylinder. The strain energy per unit area calculated from this model agrees with thut of an infinite vertical wall of edge dislocations. Based on this model, a dislocation mechanism for the shrinking of such a cylindrical boundary is proposed. The power relation between the grain boundary velocity and the driving force is accounted fm by the stress dependence of dislocation velocity. The activation area for grain boundary motion is found to correlate with that .for Creep in aluminum. In the preceding paper' the velocity of a curved grain boundary is found to be a power function of the driving force, [1] where M is the velocity at unit driving force, y is the grain boundary energy, and p is the radius of curvature. This finding adds another nonlinear rate equation to metallurgical phenomena. While a macroscopic theory for the steady state as just presented2 can be used to understand the shape of the moving boundary, such theory usually does not provide any information about the atomistics of the process. It is attempted in this paper to discuss the nonlinear rate equation in terms of a dislocation mechanism. A DISLOCATION MODEL FOR A CYLINDRICAL TILT BOUNDARY Before a dislocation mechanism can be proposed for the motion of a cylindrical tilt boundary, it is necessary to construct a dislocation model for the boundary. For simplicity, a tilt boundary in a simple cubic lattice will be examined. Although this does not represent the situation in aluminum, it is expected that the general features will be similar. The details of the model in the fcc lattice can be constructed when a refinement of the simple model is called for. A cylindrical low angle tilt boundary in a simple cubic lattice is shown in Fig. 1. Two sets of edge dislocations are needed as shown. A schematic representation is shown in Fig. 2(a). In terms of a continuous distribution of dislocations, the density of dislocations n, of Burgers vector b, in the small segment ds of the grain boundary is Similarly the density of dislocations n, of Burgers vector bz in the same segment ds is where is the tilt angle of the grain boundary. Based on this continuous distribution of dislocations in the grain boundary, it can be shown that the interaction between a small segment of the boundary and the rest of it is zero. Furthermore, the stress produced at any point inside or outside the cylinder is also zero. This shows that the model is acceptable in the sense that the boundary has no long-range stresses. Since the model of continuous distribution of dislocations in the grain boundary does not reveal the interactions among individual dislocations, a discrete dislocation model has to be used for such purpose. For simplicity, an equivalent model is shown in Fig. 3. This arises because the total Burgers vector is, from

Jan 1, 1970

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By M. J. Marcinkowski, K. S. Raghavan, A. S. Sastri

A detailed transmission electron microscopy investigation was carried out in connection with a manganese Hadfield Steel. At small plastic strains, numerous individual intrinsic stacking faults are observed. With increased plastic deformation, the stacking faults thicken into twin lamellae which in turn subdivide the original austenite matrix into smaller domains. The twin boundaries act as strong barriers to subsequent dislocation motion and is in a sense equivalent to grain refinement. It is this "grain refinement" which is believed to be the cause of the very high work hardening rates in the Hadfield Steels. In many cases, especially where an hcp phase is the stable one at low temperatures, the stacking fault energy in fcc metals and alloys decreases with decreasing temperature.' Since stacking faults of the intrinsic type are precursors of both twins as well as the hexagonal close packed structure, both of these entities should become more frequent as the temperature of a fcc crystal is lowered. In the case of the twin, there is no chemical driving force for its formation and it is generally necessary to provide the required driving force by an applied stress, i.e., strain energy. In the case of the hcp structure the transformation from the fcc modification can occur spontaneously (marten-sitically) since a decrease in chemical energy does in fact occur; however, an applied stress will provide an even greater driving force toward complete transformation. Since the transformation products mentioned above occur in an inhomogeneous manner throughout the crystal and since these can act as potential barriers to further plastic deformation2 marked strengthening effects can be anticipated. Also because metal and alloy strenghening is in general proportional to the shear modulus, these effects should be greatest in steels of the austenitic type (y), i.e., the fcc types. Perhaps the two most important steels in this category are the austenitic stainless steels and the Hadfield manganese steels. Both may be quenched from elevated temperatures so as to retain the austenitic states characteristic of those temperatures. The effect of subsequent deformation at lower tem- peratures has a profound effect on the stress-strain curves of these alloys. In particular Fig. 1 shows the compressive stress-strain curves obtained with an 18-8 stainless steel which was quenched from 1850°C after annealing for 1 hr so as to produce all y. As the temperature is lowered, the work hardening rate increases markedly. Although some hcp or c mar-tensite can be generated by plastic deformation as the temperature is lowered,~ it is believed to be a transition phase4 and most of the martensite produced is of the bcc or a variety.3 It is this stress induced martensite which gives rise to the very low initial work hardening at 77°K as can be seen in the stress-strain curve in Fig. 1. Similar low initial work hardening rates have been observed in the stress induced Ni-Ti martensites.5 Fig. 2 shows that an even more rapid rate of work hardening occurs in the Hadfield steels treated in the same way as that described for the 18-8 stainless steels a; the temperature is lowered. It is this ability to work harden to such high stress levels that makes the Hadfield steels particularly suitable for armor plate and heavy construction equipment. However, unlike the case of Fig. 1, no initial low rate of work hardening is observed in any of the curves in Fig. 2. Thus the stress induced formation of any low energy martensite phase in any significant quantity must be ruled out. This observation is in accord with the X-ray findings of Otte.~ On the other hand, small quantities of the E phase have been observed by other investigators using transmission electron microscopy (TEM) above Even more significant was the fact that large numbers of deformation twins were observed in the deformed Hadfield steels,678 which were postulated to be one of the reasons for the high work hardening ability of this class of steels.8 It is the purpose in what follows to discuss a series of experimental observations pertaining to the stress induced transformation in a Hadfield steel and to formulate a dislocation mechanism which adequately accounts for the observed results. EXPERIMENTAL PROCEDURE The stainless steel used to obtain the curves shown in Fig. 1 was of the AISI Type 303 containing approximately 18.0 pct Cr and 8 pct Ni. On the other hand, the Hadfield manganese steel used to obtain the curves shown in Fig. 2 contained between 1.00 to 1.25 pct and 11.5 to 13.5 pct Mn. In all cases the samples were in the form of compression cylinders 0.220 in. in diam and 0.370 in. long. Prior to testing the samples were annealed for a hr at 1050°C and rapidly quenched into a brine solution. This treatment was sufficient to preserve the y phase for subsequent testing at lower temperatures. All samples were compressed in an Instron testing machine using a cross head speed of 0.02 in.

Jan 1, 1970

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y&apos; (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y&apos;. At high temperatures the flow stress is controlled by the amount of Y&apos; in the alloy, i.e., the higher the volume fraction of y&apos;, the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y&apos;. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y&apos; has been correlated with changes in distribution of both the dislocations and y&apos;. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y&apos; precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y&apos;, based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y&apos; varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y&apos; nickel-base alloys is obtained when the state of dispersion of y&apos; is such that dislocations are forced to cut through the y&apos; particles at the onset of yielding. When the spacing between the y&apos; particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear&apos; in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y&apos; particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested&apos; to account for the temperature insensitivity of the flow stress is the volume fraction of y&apos;. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y&apos; in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y&apos; volume fraction was small (less than 0.2) and the y&apos; particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y&apos; at 900°C was varied from 0 to 100 pct with the y&apos; particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y&apos; and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y&apos; phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y&apos; by volume percent. (The size of the y&apos; particles produced during the equilibrium aging treatment increased as the volume fraction of y&apos; increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y&apos; phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-&apos;. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.&apos; sturkey,&apos; however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.&apos; The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,&apos; but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By J. B. Wagner, p. Hembree

The iron tracer diffusion coefficient of umstite has been measured at 110(fC across the phase field and at a single composition at 800°C. Assuming a simple cation vacancy model the tracer diffusion coefficient was found to be a linear function of the cation vacancy concentration at 1100°C. The equation is D = 3 x 20 29 where denotes the concentration of vacancies in numbers per cc. The tracer work at 800°C was carried out to investigate the reported "pinning" of tracer to the wustite surface at low temperatures. No evidence for the "pinning" of the tracer was found at 800°C in COz-CO gas mixtures. HIMMEL, Mehl, and Birchenall,&apos; Carter and Richardson,2 and Desmarescaux and La combe3 have measured the diffusion of iron tracer in wustite at several temperatures and compositions. The present work was undertaken to extend the measurements over a large composition range at 1100°C and to resolve certain apparent discrepancies in the data, expecially at lower temperatures. EXPERIMENTAL Wustite was prepared by oxidizing rectangular iron plates* in C02-CO mixtures. The samples were •The iron was supplied by the Battelle Memorial Institute courtesy of the American Iron and Steel Institute. The analysis is presented in Table I. quenched. Due to the inward flow of cation vacancies during oxidation, the center of the sample contained a thin void. The edges of the wustite slab were sanded until the sample could be split into two parts. Each part was then sanded on the front and back flat area until a smooth surface was obtained. The specimens were then replaced in the furnace and equilibrated at llOO°C in a predetermined COa-CO mixture by methods described elsewhere.4"6 The specimens were again quenched and the surfaces were lightly sanded to remove any roughness following the first equilibration. The specimens were then reequi lib rated in the same C02-CO mixture for thirty minutes in order to relieve any mechanical damage on the surface due to the polishing. The specimens were then quenched and the tracer was applied by an electroplating technique. The work of Carter and ~ichardson&apos; demonstrated that there was no systematic difference in the iron tracer diffusion coefficient in wustite if the tracer was plated, dried, or evaporated on the specimen. In the present study a piece of filter paper was saturated with an iron chloride solution of pH <* 3 that contained the tracer FeS5. The wustite was placed on the filter paper and made the cathode. A current density of 0.4 to 0.6 ma per sq cm was passed for about five to ten minutes. The thickness of the tracer layer was estimated to be about 7 x lom6 cm. This estimate was made by considering the area plated, the current flow, and time for plating and the activity of the iron in the plating solution. Different areas of the specimen were counted using a collimator to determine the uniformity of the tracer. Any specimen which exhibited a variation from the initial count rate (about 1500 cpm) by more than 15 pct was rejected. An estimate of the time necessary to convert the thin layer of iron tracer to wustite was made using the data of Pettit and wagner." he estimated time was 1 sec at 1100°C assuming linear oxidation kinetics. The shortest diffusion anneals were 1800 sec. The samples were suspended in the hot zone of a furnace by two platinum wires. Two separate specimens were run at the same time. Only the edges of each sample were in contact with the wires. The C02-CO gas of the same composition as that used in the pre-diffusion anneals flowed freely around the samples at a linear velocity of 0.9 cm per sec. To initiate a run, the specimens were lowered from the cold zone of a furnace to the hot zone by a magnetic lowering device." bout 60 sec were required for lowering. To terminate a run, the sample was withdrawn from the hot zone to the cold zone. Time zero for the beginning of the experiment was taken when the sample blended into the red glow of the furnace and conversely for the end of the experiment. The surface decrease method of measuring the tracer diffusion coefficient was used to collect the data. This method requires that counting geometry be reproducible because the specimen is counted before the diffusion anneal and after the anneal. A special jig was constructed for each specimen so the specimen could be removed from the jig and returned to the jig such that the well geometry was reproducible.

Jan 1, 1970

By J. R. Cahoon, H. W. Paxton

The mechanical properties of unidirectionally solidified A1(rich)-Mg and A1(rich)-Cu castings containing up to 15 wt pct solute have been determined with re -spect to the volume fraction of interdendritic eutectic. Pioperties were determined in the directions pumllel and Perpendicular to that of solidification; the volume fraction of eutectic was varied between the "as-cast" and equilibrizcm amounts by approperiate heat treatment following solidification. The principles of fiber strengthened composites and dispersion strengthened materials are adapted to explain the mechanical properties of these castings. It is generally accepted that castings often have inferior mechanical properties when con~pared to wrought products. However, there is little quantitative data available concerning the factors which make apparently sound castings weak and/or brittle. The relative ease and inexpensiveness of the casting process have always been attractive and, therefore, an understanding of the factors which contribute to the mechanical properties of castings would seem desirable. Such an understanding may lead to an improvement in the mechanical properties to an extent where castings would become competitive in applications where presently only wrought products are considered to have the requisite properties. Such an understanding could also improve the reliability of present cast products. Much of the recent research on castings has centered about determining the extent of segregation in cast alloys. Macrosegregation, particularly inverse segregation, has been studied in some detail 1-8 and a considerable understanding of microsegregation has been obtained.9&apos;10 The effect of solidification rate on dendrite spacing and on the amount of interdendritic eutectic in binary alloys has been established, particularly for Al(rich)-Cu alloys.""0 However, the extension of these ideas to relate the amount of interdendritic eutectic, concentration gradients, micro-segregation, dendrite spacings, and so forth, to the rnechanical properties has been limited. Dean and spear" have related the mechanical properties of an Al-Si-Mg alloy, A356-T62, to the dendrite spacing and have shown that the mechanical properties improve with decreasing dendrite spacing. Passmore et al.12 have shown that annealing at high temperature improves the mechanical properties of Al(rich)-Cu al- loys and Archer and Kempf 13 have shown that an Al-1 pct Mg-1.75 pct Si alloy behaves in a similar manner. Ahearn and Quigley 14 have shown that high temperature homogenization also enhances the mechanical properties of an SAE 4330 steel. However, in the above investigations, no underlying reasons were suggested for the improvement in mechanical properties. The purpose of the present investigation is to relate the mechanical properties of castings to some of the solichfication variables and to derive some equations by which calculations of the mechanical properties may be attempted. In particular, the effect of the amount of interdendritic eutectic and the effect of stress direction with respect to that of solidification on the mechanical properties will be considered. The Al(rich)-Mg and Al(rich)-Cu binary alloy systems were chosen for study. The A1-Mg system was chosen because its constitutional relationships are such that large volunles of eutectic (up to 24 vol pct) may be obtained in the as-cast condition and then be completely dissolved by subsequent heat treatment at about 440°C. This allows a comprehensive study relating the mechanical properties of castings to the amount of interdendritic eutectic. Also the Al(rich)-Mg eutectic is almost a single phase 15 which should make the experimental results more amenable to theoretical interpretation and calculation. The A1-Cu system was chosen for study because of the large amount of related information available concerning segregation, dendrite spacing, and so forth. Unidirectionally solidified castings were used throughout the investigation so that the effect of solidification direction with respect to the direction of applied stress could be determined. THEORETICAL It is well known that upon solidification of binary alloy castings, the nonequilibrium amount of eutectic which forms is given by 10 where fe o is the weight fraction of eutectic, Cs is the solid solubility of solute at the eutectic temperature, k is the equilibrium partition coefficient, and C, is the average composition of the alloy. In the development of Eq. [I], it is assumed that the effects of inverse segregation and diffusion in the solid are negligible, and that no porosity is present. If the casting is homogenized at a high temperature for a long period of time, some (or all) of the eutectic is dissolved and the amount of eutectic for this "equilibrium" condition may be calculated directly from the constitutional diagram. By appropriate intermediate annealing, the

Jan 1, 1970

By J. R. Cahoon, H. W. Paxton

The possibility of using unidirectionally solidified, two-phase alloys as an approximation to fiber composite materials is investigated. The short-term me.chanical properties and failure modes of unidirectionully solidified A1 (rich)-Cu alloys containing ap -Proximately 0, 17.5, and 27.7 vol pct of 0 phase &apos;fibers" are determined at temperatures from 25" to 500" and compared with those obtained for conventionul SAP alloys. In a previous publication,&apos; hereafter referred to as I, the possibility of understanding some of the room-temperature mechanical properties of unidirectionally solidified castings was explored. For Al(rich)-Cu and Al(rich)-Mg two-phase alloys over a substantial range of compositions, the yield and ultimate strengths and common ductility measures were very adequately predicted from the principles of fiber strengthening4 and the analysis of ductility outlined by Gurland and Plateau." The results obtained in I suggest the possibility of using unidirectionally solidified, two-phase alloys to simulate fiber composite materials where the inter-dendritic second phase or constituent acts as the reinforcing material. Recent attempts concerning the fabrication of fiber conlposites have concentrated on producing composites with a good bond between fiber and matrix and with very long fibers so that their maximum contribution to the strength of the composite may be realized. However, these objectives are difficult to attain in practice and present fabrication processes are either extremely laborious or costly.13 The slow, unidirectional solidification of eutectics has received considerable attention as a method for producing composite materials. 5,6 This method can fulfill both of the above objectives but it is currently laborious, expensive, and has the additional disadvantage that the volume fraction of reinforcing phase cannot be easily varied. On the other hand, unidirectionally solidified, two-phase alloys, also with a good bond between the phases, are relatively easy to make and the volume fraction of reinforcing "fibers" can be easily varied by changing the average composition of the alloy. The disadvantage of the cast alloys is that the mechanical effectiveness of the "elongated interdendritic reinforcements" (EIR)* may be reduced due to their rela- tively short lengths, the w factor in Eq. [2] of I. However, if the EIR have a high strength their contribution can be considerable. For composite materials containing discontinuous cylindrical fibers of various lengths the ultimate strength is given by1 where it is assumed that the composite fractures when the fibers fail. In Eq. [I], a, is the stress in the matrix just prior to failure of the composite, Vf is the total volume fraction of fiber reinforcing constituent, Vf(l+) is the volume fraction of fibers whose lengths exceed the critical length, I,, which is defined as the shortest length of fiber in which the stress can build up sufficiently to break the fiber. af is the fracture strength of the fiber material, w is a factor accounting for the discontinuity of those fibers whose lengths exceed I,, 1-/d is the average aspect ratio of those fibers whose lengths are shorter than I,, and t is the shear stress in the matrix at the fiber-matrix interface. The factor w is dependent on the length of the fibers and also on whether deformation of the matrix occurs plastically or elastically. However, for a given length of fiber, w is smaller when elastic deformation of the matrix is assumed.&apos; It is of interest to consider the properties of simple unidirectionally solidified, two-phase alloys at elevated temperatures in view of the possibility of using suitable modifications for high temperature service. Knowledge of the creep behavior of these materials is still rudimentary (although under active investigation) and the present paper concerns itself with short time tensile properties of some alloys similar to those investigated in I (i.e., unidirectionally solidified Al(rich)-Cu alloys). Unidirectionally solidified alloys containing 5.6, 17, and 23 wt pct Cu were tested parallel to the direction of solidification at temperatures from 25" to 500°C. In the present investigation, the alloys were homogenized for 2 days at 535°C giving a matrix of homogeneous a phase (5.2 wt pct Cu) and an interdendritic constituent (EIR) which was completely Q phase (53 wt pct Cu). EXPERIMENTAL Alloys of nominal composition 5.6, 17, and 23 wt pct Cu (containing approximately 0, 17.5, and 27.7 vol pct 8 phase, respectively, after homogenization at 535°C) were prepared by melting 1200 g of A1 (99.99 pct) in a high purity graphite crucible and adding the appropriate amount of freshly cleaned copper chips (99.9 pct). The molten alloy (at 700°C) was poured into a preheated graphite mold (also at 700°C) and the ingot unidirectionally solidified by impinging water on the steel baseplate of the mold. The alloy was degassed immediately

Jan 1, 1970