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By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By R. T. Torgerson, W. A. Baginski

Alloying studies were conducted on modifications of Cb-10W-1OHf (C-129) alloy as part of a cooperative alloy development effort between The Boeing Co. and the Wah Chang Corp. The purpose of these studies was to develop a fabricable, high- strength columbium alloy with superior melding properties. The initial investigations of alloy modifications were conducted using laboratory-melted button ingots. An alloy with the composition exhibited excellent veld ductility, elevated-ternpevature strength, and fabricability. The yttrium-modified alloy was desigrzated C-129Y and was selected for further developrnetzt. Three prodziction heats of C-129Y weve processed into sheet. Welding, forming, and tensile proper-lies are presented for this material. Tungsten-are welds of. C-129Y exhibited a minimum bend radius of 1/2T in the as-welded conditioti compared to 8T for C-129 alloy. An investigation was conducted on Disil coating of C-129Y and test data are presented on oxidation resistance and effects of re-entry environments. The excellent combination of strength, fabricability, weldability, and low transition temperature of C-129Y alloy offers potential design advantages for use of this alloy in structures of aerospace vehicles. It is atiticipated that C-129Y will rapidly supplant C-129 and similar alloys clue to the versatility provided by its impvoved welditzg properties. COLUMBIUM alloys with improved properties are required to achieve better performance and efficiency of radiation-cooled structures for re-entry vehicles and recoverable launch systems. Cooperative work by The Boeing Co. and the Wah Chang Corp. resulted in the development several years ago of C-129 alloy, a high-strength Cb-W-Hf alloy.' This alloy has received favorable consideration for many advanced designs of high-temperature structures due to its excellent combination of properties. However, this alloy exhibits low weld ductility unless given a high-temperature stress-relief treatment. For this reason the development effort was directed towards modification of the C-129 alloy composition (Cb-1OW-1OHf) to eliminate the need for post-weld heat treatment. This paper describes the successful development of an alloy meeting this requirement. This new alloy was designated C-129Y and has a nominal composition of EXPERIMENTAL PROCEDURES Alloying Studies. Various Cb-W-Hf compositions were investigated using are-melted button ingots. These buttons were hot-forged using a protective glass coating and rolled into sheet specimens. Metal-lographic examination: tensile testing, and welding studies were conducted to evaluate properties of the experimental alloys. Sheet Fabrication. Three pilot production heats of C-129Y were fabricated into sheet to establish processing techniques and to determine sheet properties. The three heats consisted of 6-in.-diam ingots weighing from 140 to 250 lb. The ingots were prepared by electron-be am melting followed by vacuum-arc melting. The hafnium and yttrium additions were made during the are-melting operation by tack welding alloy strip additions to the Cb-W master-alloy electrode. The final ingots were machined into billets with samples of the machine turnings collected for chemical analysis. Ingot breakdown methods for the three heats are as follows: Ingot Ingot Heat Size Weiaht___Breakdown Method A 6 in. 250 lb Hot extrusion B 6 in. 140 lb Hot forging C 6 in. 250 lb Hot extrusion Sheet bars from the extrusion and forging operations were conditioned, recrystallized, and rolled into sheet. Initial rolling was conducted at elevated temperatures and final rolling was conducted at room temperature.

Jan 1, 1967

By E. Buehler, R. H. Willens

A Hew melting technique has hem adapted to the rapid quenching of- alloys from the liquid state. The inelting method has no limitations on the alloys investigated for there is no reaction with crucible materials and the most refractory materials are easily melted. The vate of heating is so rapid that alloys which have a high vapor pressure constituent can be melted with a minimal loss in material. Several new superconductovs have been discoveved by vapid quenching of lolten alloys. THE rapid quenching of alloys from the liquid state has led to the discovery of many new metastable phases. The methods initially used were limited to alloys which did not react with crucible materials.1,2 There was also the unmentioned limitation in tem- perature. Alloys with melting points much greater than 2000°C could not be melted in the rapid-quench apparatus. Recently, there have been successful attempts to rapidly quench reactive alloys by Moss et at. and Matthias Moss et al. injected powdered material (325 mesh) into a high-temperature plasma and the high-velocity molten droplets impinged on a cooled copper plate. The technique innovated by Matthias was to melt the alloy in an arc furnace and splatter it against a copper plate by means of a high-velocity gas jet aimed at the melt. I) FAST COOLING APPARATUS The creation of a metastable phase in a given alloy system by rapid cooling from the melt is contingent on the quenching rate. Some alloys require very slow rates while other alloys require the ultimate in quenching rate. At the present time, the vertical-gun technique of Duwez and willens' has demonstrated, in practice, the highest quenching rates and thus the best

Jan 1, 1967

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By J. Campbell

The negative pressure developed within a solidifying sphere of pure iron is investigated theoretically assuming an elastic-plastic model. The maximum hydrostatic tension attainable is shown to be an order of magnitude smaller than that required for the homogeneous muclealion of pores in the liquid cove, and four orders of magnilude smaller than that predicted from) a rigid shell model. It is well-known that liquids can withstand large hydrostatic tensile stresses, or negative pressures. The various experimental investigations of the tensile strengths (often called the fracture pressures) of liquids are reviewed by Dean,1 and the theoretical attempts at estimating fracture pressures are critically assessed by wakeshima.2 Using Fisher's3 quation, the fracture pressure of pure liquid iron is about -70,000 atm, which may be too large by as much as a factor of 4, but is certainly correct to within an order of magnitude.' In view of the great importance of the problem of the nucleation of shrinkage cavities in castings it is of interest to determine exactly what tensile stresses can exist in the residual liquid in a solidifying casting; it has often been assumed that, because of the very low strengths of solid metals near their melting points, no interior stresses are developed at all. Nussey4 has determined theoretically the pressure in the liquid core of a solidifying metal sphere assuming that the solidified shell does not deform (i .e., is perfectly rigid), so that because of the contraction accompanying solidification (a) (about 3 pct for most metals) the progressive deposition of solid onto the inner surface of the shell causes the remaining liquid to be expanded to make up this difference in volume. This leads to a relation between the pressure P in the liquid, the initial pressure, PO, the bulk modulus of the liquid, K, and the inner and outer radii of the solid shell, o and b, respectively:

Jan 1, 1968

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

Jan 1, 1967

Jan 1, 1968

By J. L. Swedlow, M. L. Williams

Two standard techniques for assessing fracture initiatlon in sheet specimens involve measurements of 1) the applied load of fracture which, via linear fuacture mechanics, is used to find the fracture tough/less SC (or SIC), and 2) the velative displacement of fracture of the opposite free faces of the crack (COD). In the past, the quantitative association between these two parameters has not been determined in detail, owing to the mathematical difficulties of computing. the stress and strain fields in the combined elasto-plastic flow near the crack. Using a numerical technique Irecently developed and applied to a 7075- TO' aluminum plane stress specimern, the two parameters noted have been determined and associated quantitatirely. CONSIDERABLE effort has been expended in selecting a rigorous yet practical manner for predicting fracture. The usual point of departure is the modified Griffith criterion in which the mechanism of energy dissipation is reflected in Sc (or SIC), the parameter of "fracture toughness". Sc. differs from the surface energy used by Griffith in perfectly brittle fracture in that it includes the effect of plastic flow in the vicinity of the crack tip. Because plastic flow alters the stresses and displacements predicted from the usual linear theory of fracture mechanics, and because analysis of the nonlinear stress-strain field has presented great obstacles: only estimates of several pertinent quantities have heretofore been available. Nevertheless, two parameters have often been measured experimentally althougll usually just at the point of fracture. These are the energy release rate, or fracture toughness 9, (or I,), and the crack-opening displacement (COD). Such observations have been used in connection with frarture criteria and have been most helpful in design, although their application requires care with respect to changes in geometrical configuration from that upon which the criteria were based 1,2 Recently, however, a reasonably accurate and comprehensive method for analyzing the elasto-plastic flow has been devised and applied to plane stress specimens having arbitrary octahedral stress-strain curves.3 It thus becomes feasible to compute, albeit numerically, both the fracture toughness and crack opening as functions of the applied tensile loading on a typical specimen geometry. As a result, it is now possible to associate these two parameters quantitatively, and thereby to associate data obtained by one method with data pertaining to the other. ELASTIC ANALYSIS For the case of linear elasticity, it is relatively easy to deduce the connection between various measures of crack deformation. Using, for example, the singularity analysis, it is found that the leading term of the Airy stress function x f°r symmetrically applied loadings on an isotropic medium is

Jan 1, 1968

By R. E. Hook, R. L. McGaughey, A. M. Adair

The initial yielding characteristics of a vacuum-melted iron have been measured as a function of thertnal history after slow cooling or quenching from a 700°C recrystallizntion anneal. A thermal history favoring the segregation of interstitials to grairz boundaries results in a material having high values of upper and lower yield stress and long, irregutar Luders' plateaus, wheueas specimens treated to minimize grain boundary segregation have significantly lower values of these yielding characteristics. The struc- ture of typical grain boundary areas as revealed by electron transmission microscopy is consistent with these findings. The grain boundaries in iron are considered to be principally responsible for the release of dislocations during macroscopic yielding and it is suggested that strong locking results when a substantial amount of grain boundary segregution is present; it follows that weak locking results from a more random distribution of interstitials to grown in dislocations. RECENT years have seen an increased emphasis placed on a more quantitative study of the influence of grain boundaries on the yield behavior of bcc metals. The earlier picturk of dislocation pileups at grain boundaries building up a sufficient stress concentration to unlock dislocations in neighboring grains1

Jan 1, 1967

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By E. N. Aqua, C. M. Owens

The microstructure in cold-rolled Zircaloy-4 sheet has been characterized by transmission electron microscopy and X-ray diffraction line-broadening techniques. The rate of work hardening is measured in terms of microstrains, particle sizes, micro hardness, the tensile yield strength. The tensile yield strength of Prestrained (less than 10 pet) Zircaloy-4 sheet is found to be a linear function of the square root of the dislocation density, us predicted by work-hardening theories. ZIRCALOY is one of the most important structural alloys for nuclear reactor applications.''2 In order to understand the effects of the nuclear environment on Zircaloy structural members, the preirradiation microstructure must be characterized. This report will describe the substructure existing in cold-rolled Zircaloy-4 sheet as observed by electron microscopy and by X-ray diffractometry. I) EXPERIMENTAL PROCEDURE Commercial Zircaloy-4 strip was cold-rolled and annealed in argon at 760°C for 1 hr. The annealed sheet was again cold-rolled to a maximum of 50 pct reduction in thickness with segments of the strip being retained after 2.5, 5, 10, and 20 pct reductions. One-inch-square portions were chemically polished (50 parts HNO3, 50 parts H2O, 10 parts HF) and mounted onto lucite blocks using double-sided tape to prevent bending during handling. Thin foils suitable for transmission electron microscopy were prepared from each of the sheet samples. The sheets were mechanically polished through 600-grit paper to a 3 to 4 mil thickness and were chemically polished by immersion for 1 to 2 min in a solution containing: 50 parts HNO3, 50 parts H2O, and 10 parts HF, and rinsed in distilled water. The final metallographic procedure was to electropolish for less than 10 sec with an electrolyte of 10 parts perchloric acid and 90 parts glacial acetic acid, at 20 v, at room temperature using stainless-steel point cathodes and a vigorous stirring action. These foils were examined in a Philips EM 200 electron microscope using a 100-kv accelerating voltage.

Jan 1, 1968

By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young's modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young's modulus.' Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman' in several fee alloys and by Müller5 and others"' in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,' this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.' The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young's modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968

By Robert E. Green, Edmund G. Henneke

Expressions are derived for the orientation factors associated with dislocation damping due to dislocation motion in the basal slip plane. The results of the calculation of these factors for zinc crystals aye pvesepzted and the relevance of these results to ultvasonic-attenuation measuvements is discussed. In this paper expressions are derived for the orientation factors associated with damping of sound waves due to dislocation motion in the basal slip plane of hexagonal crystals. For zinc crystals, the orientation factors for dislocation motion in one slip direction only, as well as for simultaneous motion in all three basal slip directions, have been calculated at 1-deg intervals. The results of these calculations are presented in the form of contour diagrams in a sector of a standard polar coordinate graph. The calculations have been carried out for both the traveling- and the standing-wave conditions. The relevance of these results to ultra sonic-attenuation measurements is discussed. Associated with the calculation of the orientation factors, the modes of elastic-wave calculation were also evaluated, according to the procedure previously employed by Hinton and Green.' The results of these calculations are not presented here since similar results have been reported earlier by Mus-grave.2 However, it should be mentioned that, although the qualitative features of Musgrave's results are preserved, the quantitative values are somewhat altered since different values for the elastic constants of zinc were used. ORIENTATION FACTORS It is convenient to refer to three different sets of coordinate axes, Fig. 1, in the following calculations. First, there are the Miller-Bravais axes which are used in describing the Miller-Bravais indices of planes and directions in a hexagonal crystal. These axes are denoted in the conventional manner by a,, a,, a,, and c. The second set of axes used is a rectangular Cartesian coordinate system located as shown in Fig. 1. Note that the x axis coincides with the close-packed direction al [2110], the z axis coincides with the c axis [0001], and the y axis is orthogonal to these two lying in the [0110 ] direction. Finally, a form of Eulerian angles is used to locate the position of the specimen axis. The angle between the specimen axis and the c axis is denoted by 0 and the angle between the projection of the specimen axis on the basal plane and the a, direction is denoted by ø. The majority of observations on plastic deformation of metal crystals indicates that such deformation is caused by the motion of dislocations on a limited number of crystalline planes and in a close-packed direction. In crystals with hexagonal symmetry the most prominent slip plane is the basal plane (0001) and the slip directiops- are one of the close-packed directions, [2110], [ 12101, or [ 1120]. To properly set the stage for the following work, several points must be clarified. First, we want to consider the contribution to the attenuation of elastic waves by dislocations only. While the Granato-Lucke, model for dislocation damping is presently the one most quoted, it is not necessary to refer the present work to it. The only assumption that need be made is that the motion of dislocations absorbs energy from the elastic wave and therefore attenuates it. It is immaterial here how this energy absorption occurs. However, because dislocations have been observed to move most freely on the (0001) plane for hexagonal crystals undergoing plastic deformation, it will be assumed that it is the dislocation motion on this plane which attributes to the observed attenuation. The basic orientation factor, Ok, is essentially the same as that used by Green and Hinton for fee crystals,4 defined by the equation

Jan 1, 1968

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By David R. Poirier

THE activity of carbon in Fe-C-Cr liquid solutions has been measured by Richardson and Dennis,1 Fuwa and chipman,2 and Goto et aL3 Fuwa and Chipman2 have presented their data along with data of Richardson and Dennis1 and utilized an interaction parameter. However, the interaction parameter is only valid for dilute solutions of carbon, because, as indicated, the same interaction parameter does not apply to more concentrated solutions of carbon (i.e., the effect of chromium on the saturation of graphite in liquid iron). Ohtani4 has attempted to account for the effect of carbon concentration on the interaction parameter; however even his analysis does not apply to the saturation data. Also, the effect of temperature on interaction parameters must be taken into account. Therefore, in any process where the concentration of carbon and/or the temperature changes (such as solidification), the use of an interaction parameter is not adequate to know the activity of carbon. The purpose of this communication is to make use of the existing data on the effect of chromium on the activity of carbon in liquid iron solutions in such a way that the activity can be described as a function of both composition and temperature. The method is an extension of Rist and chipman's5 analysis for the binary Fe-C solutions. As in Rist and Chipman's analysis, the activity coefficient is assumed to obey the relation: log y1 = at(l -X1)2 + It [1]

Jan 1, 1969