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By G. R. St. Pierre, L. M. Adelsberg, R. Speiser

The rate of scale fot'~I~ti0n on tantalum held in H20-Hz-Ar gns mixtures at temperatures between 840" and 1250°C is related to gas composition and ternpevature. It is found that water vapor partial pressure determines the oxidation rate at a given temperature and that the oxygen potential as fixed by the water vapor to hydrogen ratio Ins no significant effect on the oxidation rate. The Ta205 scale formed during oxidation is composed of an inner lattice-dijf~ision barrier and an outer layer of- cracked/porous oxide 1 HE oxidation of tantalum at temperatures less than 800°C is characterized by solution of oxygen into the metal,'-' the formation and growth of suboxides into the metal,')2~10-15 and the delayed nucleation of the highest oxide, Above 800°C, Ta205 is found to nucleate rapidly10, 11, 15, 16 except at low oxygen pressures:15 however, there is uncertainty regarding which does not retard the oxidation process. For each gas con~position and temperature investigated, the oxidatioz rate becomes constant after a short adjustment period. It is shozm that a constant oxidation rate nzay pre~?ail even though the tlzickness of the inner lattice-dijjitsion layer of Ta205 is clanging. TFze initial czcrz!ature of the typical 'Paralinear" oxidation curve may result froprz causes other than an increasing thickness of tlze inner protective layer. the detailed mechanisms of the high-temperature oxidation. Peterson, Fassell, and wadsworth17 observed linear oxidation behavior for tantalum in oxygen at temperatures between 600" and 1000°C. They reported that equilibrium adsorption of 0, occurs on a surface prior to the rate-deter mining step of the reaction. Cowgill and stringer1' confirmed the observations of Peterson and his coworkers. They stated that the rate-determining step of the reaction could be either the incorporation of adsorbed oxygen into the anion lattice or the dissociation of 0, at the gas-oxide interface. The relative rates of the two surface reactions were proposed to be dependent upon the reaction temperature and the oxygen pressure. stringerlo subsequently reported that the reaction surface is located somewhere

Jan 1, 1968

By David L. Sikarskie

The measurement of residual stress fields using X-ray diffraction techniques requires the removal of successive layers of material from the specimen. In the process of removing these layers, the underlying residual stress field is altered; hence, if the original stress field is desired, corrections must be made to the measured stresses. Although these corrections already exist for a number of cases, an alternate procedure is outlined herein whereby the corrections are presented in series form. This form is numerically more convenient within certain ranges of correction depths and in its simplicity gives additional insight into the factors affecting the corrections. It, further, readily permits determining the proper slice depth to remove and the effect on the correction of both specimen thickness and magnitude and form of the measured residual stress itself. ONE of the techniques currently being used to determine residual stress fields is X-ray diffraction. Since X-rays are diffracted essentially from the layers of atoms near the surface of the specimen, of the order of 0.0001 to 0.001 in. depending on conditions, the method can only determine stresses* in this very thin surface region. Therefore, if the residual stress field at some depth into the specimen is required it is necessary to remove successive layers of material taking measurements after each cut. In the process of removing a thin surface layer of stressed material, however, the over-all equilibrium of a cross section of the specimen is disturbed with the result that the internal residual stress which existed before the slice of material was removed is altered. This alteration of stress occurs after each slice and its effect is cumulative. Thus, if the original stress distribution is desired, corrections must be applied to the measured stresses. These corrections can be found by satisfying equilibrium on each new cross section. These corrections have been derived in detail for a number of cases, e.g., cylinders, bars, plates,' and also are given in Appendix VI of Ref. 2. In each of the above cases the correction terms require the evaluation of definite integrals of the measured residual stress distribution. In general, this is indeed the way one would proceed with the corrections. There are a number of instances, however, where the integrals can be replaced by a series form of correction which is considerably more convenient numerically and, also, gives added insight into the factors which influence the corrections. Such a form of the correction is particularly useful, for example, if one is interested in designing a test such that stress corrections will be small. Also, the question of what depth of slice to use in relation to both specimen thickness and residual stress distribution itself must invariably be answered. Questions of this type can be readily answered using a series form of correction. In addition, if the correct residual stress distribution is needed only for limited depths into the specimen the series correction provides numerical results which are equivalent to the integral correction. I) DERIVATION OF THE SERIES CORRECTION The problem to be considered here is that of a bar or plate,* i.e., either one or two dimensions of the specimen is large compared with the third. Also, the residual stress distributions considered depend only on z, see Fig. 1. In view of this it can be shown' that a stress correction, based on simple beam theory, satisfies all conditions of "elasticity theory" and hence is the correct (and only) solution. The integral form of the correction (this assumes that the measured residual stress is a piecewise continuous function) as given in Ref. 1 is:

Jan 1, 1968

By W. A. Tiller, S. O’Hara

Grain refinement in stirred melts has previously been shown to arise from dendrite segmentation. The present work discusses experiments capable of distinguishing between remelting and mechanical effects which result from fluid motion. Nucleation of still un-dercooled Sn-1 pct Pb melts with a single-crystal seed shows that the grain size of the resulting ingots decreases as the undercooling at nucleation increases up to about 1Z0C, then increases again for larger undercoolings. Pure melts exhibit little refinement as a result of nucleation at any undercooling up to 12°C. The presence of fluid motion gives rise to grain multiplication in pure melts, but the magnitude of this effect is partly obscured by solid-state pain growth. The results indicate that two grain-multiplication pvocesses can operate, one which involves dendrite remelt ing, and another associated with fluid motion. Small ingot experiments indicated that an equiaxed transition can be caused by fluid motion. THE presence of forced convection during recales-cence of undercooled Sn-1.3 pct Pb melts has been shown to give rise to extensive grain refinement during solidification of small ingots of this alloy.''2 In Ref. 2, this refining was shown to result entirely from dendrite fragmentation and not from any nucleation mechanism. The purpose of the present work is to establish what processes lead to dendrite segmentation. Experiments were therefore carried out to determine the resulting structure of both pure tin and Sn-1 pct Pb melts, nucleated at various undercoolings by single-crystal seeds in the absence of forced or natural convection. By comparing the information obtained from these experiments with the results of Refs. 1 and 2, the effects of fluid motion on the ingot structure, and the details of the segmentation mechanisms, should become clear. The results of these experiments should also be helpful in understanding the solidification structures of larger ingots since natural convection, which is known to play an important role in determining ingot structure13 differs only in degree from the fluid-motion effects studied here. I) EXPERIMENTAL PROCEDURE The apparatus shown in Fig. 1 was constructed to permit controlled nucleation of stirred or unstirred supercooled melts using a seed oriented in the tin dendrite growth direction. Because the melts, in all cases, were capable of larger supercoolings than the one used in each experiment, the structure observed always resulted from a single nucleation event at the surface. The sequential procedure was as follows: Tin was melted under purified hydrogen and the oxide removed at a temperature of 450°C . Electromagnetic stirring was then used to clear the surface completely and during this time the guide tube was lowered underneath the melt surface. A pointed Czochralski-like crystal was then propagated from a specially prepared tin dendrite seed4 inside the guide tube while the temperature of the bulk melt was held just above the melting point, ensuring a perfectly clean seed which was epitaxial with the original dendrite. The dendrite and epitaxial seed, still in the guide tube, were withdrawn from the melt which, in turn, was undercooled to 2C° below the temperature at which the nucleation experiment was to be performed. The melt was held there for several minutes, both in stirred and in still-melt experiments. The temperature was next raised to the required value and the melt nucleated by the carrot seed inside the guide tube, the heater power being shut off just after nucleation. In experiments where quenching after nucleation was required, a high-density graphite crucible was used, but otherwise the procedure was as described above. The temperature gradient in the melt before nucleation was kept below 1C° per cm by carrying the experiment out just below the center of the heater shown in Fig. 1.

Jan 1, 1968

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By A. D. Zunkel, A. H. Larson

Equilibrium antimony contents of pb-sb alloys in contact with PbO-Sb2O3 slags containing less than 45 mole pct Sb203 uleve determined at 650&apos;, 700°, and 750°C in an inert atmosphere. In this ten~pevature range, the antimony contmzt of the alloy increased with increasing temperature at all slag compositions. The PbO-Sb203 phase diagram below 28 mole pct Sb2O3 was determined by thermal analysis and by application of a log sbZ4/y$b0 us plot determined from the equilibrium-activity data. The resulting phase diagram showed a eutectic at a temperature of 604°C and a comfiosition of 21.6 mole pct Sb2O, with a maximum terminal solid solubility of Sb203 in PbO of 5.6 mole pct. These results are compared with existing data in the literature. In the past three decades, only a small amount of experimental work has been done on the slag-metal equilibria in the Pb-PbO-SbaO3 or the analogous arsenic and tin systems. These systems are important in commercial lead-refining processes such as softening and dross fuming since it is impurities such as antimony, arsenic, and tin in lead bullion and Sb2O3, As2O3, and SnOz in lead drosses which must be re-

Jan 1, 1968

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.&apos; EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2&apos;3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

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

A study was made of&apos; the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner&apos;s first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry&apos;s law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner&apos;s well-known expression for the activity coefficient&apos; is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors&apos;-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:&apos;&apos;

Jan 1, 1968

By I. R. Kramer

The stress associated with the surface layer was deter-minedfor iron and molybdcnum. These measurements show that the surface layer plays a very important role in the plastic deformation of bcc metals. From the relationship between strain arui the surface layer stress and the back stress imposed by the internal obstacles, it is Proposed that the term of of the Hall-Petch equation is related only THE large number of studies on plastic flow of bcc metals have failed to delineate clearly the nature of the obstacles influencing dislocation movement. Since there have been numerous articles which have reviewed the mechanisms proposed to explain various aspects of plastic flow of bcc metals (for example, conrad1 and Keh and weissmann2), no attempt will be made here to discuss their conclusions. However, it should be to the surface stress while the term Kfd is the stress required to move dislocations through internal obstacles. Further, it was possible to derive the well-known empirical equation C = , and it is shown that the terprz a is comprised of two terms: a term Cs associated with the surface layer stress and Ci related to internal dislocation obstacles. pointed out that in all of these publications it has been tacitly assumed that plastic flow occurred uniformly throughout the cross section of the specimen (except, of course, for the Luders band region), It has generally been further assumed that the nature and distribution of the obstacles opposing the motion of dislocations are of the same type throughout. The role of the surface layer in bcc metals has not, as yet, been considered even though its role in fcc metals has been shown clearly to be of primary importance.3-5 Investigations on fcc metals have shown that at the onset of plastic deformation a surface layer acts to

Jan 1, 1968

By R. W. Smashey, B. J. Piearcey

The structure, composition, and morphology of the carbide phases present in the nickel-base superalloy, Mar-M200, hare been determined and three carbide phases observed. The MC carbide is a solidification product, and the M23 Co and M6C carbides are both prod~icts of solid-state precipitation. The identity of each phase usas determined by both X-ray and electron-diffraction techn~ques. Compositions of all three carbides were studied using the electron beam micro-probe analyzer and by unalyszs of electrolytically extracted residues. Optical and electron microscopy were employed in order that the time/temperature -dependent behavior of the carbides might be observed. Supplementary studies were completed on thin foils and oriented single crystals to determine the mor-phology and orientation relationship of each phase with that of the matrix. MAR-M~OO* is a high-temperature, creep-resistant superalloy designed for use in the as-cast condition. The "as-cast" microstructure consists of a solid-solution matrix, referred to as gamma (y), which contains a general, coherent precipitate of the inter-metallic Ni3(A1,Ti) referred to as gamma prime (?). As a result of dendritic segregation during solidification, a degenerate, spherulitic ? -?&apos; eutectic constituent is present at the grain boundaries and the in-terdendritic regions, which is nucleated by the y on the dendrite tips. A primary carbide phase, a solidification product, is also present at the grain boundaries and in the interdendritic areas, and an additional carbide appears at the grain boundaries as a fine discontinuous precipitate. The alloy is particularly susceptible to heat treatment. For example, the mechanical properties of the columnar grained mater- ial are substantially improved by solution heat treatment, followed by an intermediate temperature age. Metallographic examination of heat-treated material reveals, however, that exposure to elevated temperatures has a marked effect on the microstructure of the alloy; in particular, it is observed that precipitation of considerable amounts of various carbide phases occur. The following investigation was carried out to determine the morphology, composition, and behavior of the carbides in Mar-Ma00 as an aid to the determination of their effect on the mechanical properties and stability of the alloy. THE PRIMARY MC CARBIDE The MC carbide phase appears in the interdendritic interstices and the grain boundaries. In directionally solidified Mar-M200 the carbide appears as very small particles in the chilled region, Fig. l(a), whereas in material less affected by the chill, it becomes larger and develops a dendritic morphology, Fig. 1(b). Step polishing of metallographic specimens from this region shows that in directionally solidified material the individual carbide dendrites are connected in a dendritic network within the metallic interdendritic interstices, whereas in material from the chilled region and in conventional Mar-M200 they are discontinuous, isolated dendrites. No orientation relationship exists between the primary carbide and the matrix.

Jan 1, 1968

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.&apos; However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*&apos;3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By B. A. Cheadle, K. P. Steward

Axial tensile, ring tensile, closed end burst, and free end burst tests were done at room tempe.vature and 300°C on three batches of Zircaloy-2 sheathing zuith different textures. Knoop hardness tests were also done on all batches. The mechanical properties of the tubes were largely dependent on the percentages of cold work, but were also markedly affected by the textures, particularly with respect to deformation behavio&apos;r. The deformation behavior observed confirmed Picklesimer&apos;s predictions, zuhereas Knoop hardness results could be correlated with texture and yield strength anisotropy after the ,method of Wheeler and Ireland. From the mechanical properties, and from efjectiue strain values deterrlzined at the fractures using a photoqid technique, it zuas concluded that tubing witlz a single preferred orientation of radial basal poles best combines strength and ductility for any given deqee of cold work. THE mechanical properties required in collapsible Zircaloy-2 fuel sheathing for water-cooled power reactors are strength to resist wrinkling deformation by coolant pressure and ductility to accommodate a small amount of deformation in service without rupturing. Zircaloy-2 tubing during fabrication develops pre- ferred orientations of the a Zr grains due to aniso-tropic deformation behavior, and these textures markedly affect mechanical properties. Picklesimer&apos; had predicted the deformation behavior of tubes with various textures, but the texture required to provide the optimum strength and ductility for a given degree of cold work has not been reported. To investigate this problem, tests at three transverse to axial stress ratios were done at room temperature and 300°C on three batches of Zircaloy-2 tubing covering a wide range of textures and percentages of residual cold work. Knoop hardness values were also measured to correlate with preferred orientation and yield strength anisotropy after the method of Wheeler and relland.&apos; 1) MATERIAL For this investigation, three batches of tube-reduced tubing were chosen from the Zircaloy-2 sheathing produced for the Douglas Point Reactor. Individual tubes were 191/2 in. long, 0.600 in. OD, and 0.0165 in. nominal wall thickness. The identities of the batches, together with their textures, are shown in Table I. The tubes had the normal Zircaloy-2 composition3 of 1.5 wt pct Sn, 0.3 wt pct Fe, Ni, Cr combined with the following oxygen concentrations: Batch VII 1140 to 1390 ppm 0 Batch VIII 1400 to 1750 ppm 0 Batch IX 880 to 1320 ppm 0

Jan 1, 1968

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young&apos;s modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu&apos; have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young&apos;s modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu&apos; pointed out, calculated variations in Young&apos;s modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young&apos;s modulus, the shear modulus and Poisson&apos;s ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young&apos;s modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"&apos; could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.&apos; Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,&apos; and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-&apos; per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By J. H. Bucher

The effect oj strengthening by the precipitation of CbC on the toughness offerrilic steel (0.11 pct C, 0.74 pct Mn, 0.02 pct Cb) was stlrdierl. A g-veater degree of pvecij~itatiotz strengthning is ohtaznable by aging the so11ution-treated steel rtt velaticely Low temperature was (1050" to 1l0O3F) than at higher temperatures (I150" to 1200°F). Tlzis ),eslrlts because a finer dispersion of CbC is obtained. However, the ductile-brittle transition te~ripertltlo.e is raised approximately tlzjeee tirues as IFLIIC~ perv a given yield stress increase) by aging in the lower tempareture range, as opposer1 to the Irigher temperaturee range. This is proposed to result pl-iir~avily because different precipitation distributions ar-e associated with the different aging -treaments. For tile steel aged at 1050" and 1100 F, heavy: precipitation on disloccctions occurs resulting in a high degree of rlislocution pinningh tl~us lowevirzg- the toilguiess. in tll c(.rise of the steel aged at 1150 &apos;a?zd 1300"F, Pvecipitatiol~ is irzove g-enerally distributed throughout the matrix rather limn preferentially on dislocations.; and Ike detlsitj, oj mobile dislocations is not sttyong-ly affected. THE most effective means of strengthening hot-rolled ferritic steels are grain refinement and precipitation hardening. It is well-known that grain refinement increases both the strength and the toughness. However, the upper limit of yield strength obtainable by grain refinement alone is about 60,000 psi,&apos;12 i.e., without the formation of acicular structures of lower toughness. The most economical means of obtaining higher strengths is the addition of small amounts of elements such as columbium, vanadium, and titanium which form carbonitrides. These precipitates are very effective in increasing the strength, but the ductile-brittle transition temperature is is Although it is agreed upon that precipitation decreases the toughness, there has been little effort to isolate the causative aspects of embrittlement. The purposes of this research are to assess quantitatively the embrittlement associated with different precipitate distributions and morphologies, and to correlate the degree of the embrittlement with the microstruc-ture. In this manner, a more fundamental insight into the mechanism of embrittlement may be gained. The steel selected for this purpose was a low-carbon, columbium-bearing steel which, after solution treatment, was aged in various time-temperature cycles while attempting to hold all other microstructural variables constant. MATERIALS AND PROCEDURE The composition of the steel used in this investigation is given in Table I. Starting with commercially hot-rolled material 0.074 and 0.280 in. thick, tensile blanks were cut from the thinner material and sub-size Charpy blanks from the thicker stock. The steel had been rolled using a low finishing temperature and rapid cooling after hot rolling to produce grain refinement. Also, chemical-extraction analysis and electron-microscopic examination revealed that the cooling was rapid enough to suppress any significant precipitation of CbC. Therefore, the as-rolled steel is essentially in the solution-treated condition in terms of the precipitation reaction, and it was used as the base material in this investigation. The room-temperature tensile properties of the as-rolled steel aged at 1100", 1150", and 1200°F for various time intervals were determined, see Table 11. The ductile-brittle transition behavior was studied for smooth and notched tensile specimens, and longitudinal half-size (0.200 in. thick) Charpy V notch specimens aged at 1100" and 1150°F for various times, also Table 11. In addition, tensile specimens aged for single times at 1050" and 1200°F were evaluated with respect to their ductile-brittle transition. Only one 1050°F treatment was used because of the extremely slow kinetics of precipitation at this temperature and because no significant difference between 1100°F aging was observed. Only one treatment at 1200°F was used because aging at this temperature alters the shape of the grain boundary cementite particles present in this steel and complicates analysis. The design of the tensile specimens is given in Fig.1.

Jan 1, 1968

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of- liquid Mg-Pb allojs have been determined by an isopiestic method from 18 to 42 at. pct Pb and by a thevmodynumic analysis of the phase diagram frofiz 0 to 100 at. pct Pb. In the overlapping composition range the magneszupn activity values derived by the two methods are in excellent agreement, thus mutually supporting the correctness of the Mg-Pb phase diagram previously determined by the authors and of the acticitzes deriz~ed isopiestically. SEVERAL studies have been made of the thermody-namic properties of liquid Mg-Pb alloys. Wagner and Engelhardt,1 Lantratov,2 Knappwost,3 Sryvalin et al.* and Wilson5 used the electromotive-force method, Scheil and Wolf8 and Schmahl and Sieben" applied the transpiration technique, and the present authors8 utilized the phase diagram to determine the activity of magnesium in the Mg-Pb system. The results of these studies are not in very good agreement and could not be incorporated into a general systematic analysis of the thermodynamic properties of the homologous series of the Mg-Group IV B systems Mg-Pb,8 Mg-Sn,° Mg-Ge,10and Mg-Si.11 The thermodynamic properties of the Mg-Pb system were therefore re investigated by an isopiestic technique which has been developed for similar studies in the Mg-SnB and Mg-Ge10 systems- Lead specimens, contained in iron or graphite crucibles, were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure to form alloys of compositions which depended on their temperatures, the temperature of the magnesium vapor source, and the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE Magnesium (Dominion Magnesium Ltd., Toronto, Canada) of 99.99+ pct purity and lead (American Smelting and Refining Co.) of 99.999 pct purity were used. In the early experiments, Runs 2 and 3, the alloys were contained in uncovered high-purity iron crucibles. Alloys formed in the uncovered iron crucibles had to be chemically analyzed owing to the slight volatility of lead under the imposed experimental equilibration conditions. The compositions of these alloys were determined by a gravimetric analysis of lead as lead chromate. To avoid this problem, the remaining runs were made in covered graphite crucibles machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non- i reactivity of graphite with lead and magnesium has been previously established,&apos; and the experimental procedure has been described in full detail.&apos; In the runs using covered graphite crucibles it was found that the weight increases of the crucibles and their contents after equilibration equaled the magnesium contents of the alloys within the accuracy of the chemical analysis (i0.3 at. pct Pb). Clearly, the small lid openings of the graphite crucibles prevented significant lead losses during a run, and the weight increase was therefore taken as the magnesium content of the alloys. EXPERIMENTAL RESULTS At thermodynamic equilibrium the magnesium partial pressure of the specimens equaled that of the reservoir. Since the magnesium reservoir was always maintained at the temperature minimum of the system, the activity of magnesium of any specimen was given by the ratio of the magnesium reservoir pressure to the vapor pressure of pure magnesium at the specimen temperature. The standard state was chosen as liquid magnesium and the vapor pressure of liquid magnesium

Jan 1, 1968

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.&apos; is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By D. E. Peacock, B. Harris

Thermal-expansion and electrical-resistivity measurements have been carried out below 400°K on niobium and two niobium alloys containing tungsten. For anonaly in the expansion us temperature curve below aboct 300°K. This reslt is consistent with an earlier obsercation that Young&apos;s modilus joy Cb-132 lms an unusiully strong -tenperati-e dependence below roon temperature. No anonulous behavior was observed in the resistiuity vs temperature curve for either alloy or in the magnetic susceptibility us tenperature curve for Cb-132. These results are disclssed in terms of various electronic and bonding theories of the transition metals and their alloys, but it has not been possible to reach any definite conclusion as to the cause of the results obtained. ALONG with investigations of the low-temperature mechanical behavior of niobium and its alloys, some of the physical properties of these materials have also been studied. In the work described here, thermal expansion and electrical resistivity were measured below 400°K for niobium and two of its alloys, Cb-132 and D-43. In addition, the magnetic susceptibility of Cb-132 was measured over the same temperature range. The alloys are representative of two distinct tion-hardened alloy such as might find service as a turbine blade, while D-43 (Nb, 5.3 at. pct W, 1.1 at. pct Zr. and 0.08 at. pct C) is a solution- and dispersion-hardened alloy, of considerably lower strength than Cb-132. which is a potential vane material. Their significant common feature is the presence of tungsten as the principal source of solution hardening. EXPERIMENTAL TECHNIQUES Thermal-expansion measurements were made with a quartz-tube dilatometer using baths of liquid nitrogen, liquid bromoethane, and a liquid polyalkylene glycol derivative to cover the range 80 to 400 K. Results are recorded as expansion relative to that of quartz, and the probable maximum error in any value of relative expansion. All, is about il pct. The metallurgical condition of the specimens, which were in rod form. will be discussed in the section dealing with experimental results. Resistivity was measured on recrystallized wires 0.030 in. in diam using a potentiometric technique. The same baths were used for temperatures between 80&apos; and 400°K as were used for the expansion measurements. and in addition the resistance of D-43 and Cb-132 was measured at 4.2 K by immersion in liquid helium. The maximum expected experimental error in any resistivity value is about 3 pct and that in any change in resistivity about i0.05 pct. Temperatures in both sets of experiments were measured with liquid-in-glass thermometers with an accuracy usually better than 1°K. EXPERIMENTAL RESULTS 1) Thermal Expansion. In Fig. 1 is shown the relative linear expansion of recrystallized niobium. D-43. and Cb-132. The curve for Cb-132 is composed of results from several runs on three different samples. Two of the samples were annealed for an hour at 1500°C to cause recrystallization and the third was annealed for an hour at 2000&apos;C to remove some mi-crosegregation of tungsten which was known to be present in the wrought alloy received from the manu-

Jan 1, 1967