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By J. C. Coughlin, M. C. Flemings, T. Z. Kattamis

Experiments on Al-4.5 pct Cu alloy shou the dendrite arnz spacing increases with time during isothermal holding in the liquid-solid region. This coarsening of the dendrite structure is then shown to occur at roughly the same rate during solidification as during isothermal holding. Final dendrite arm spacing in both types of experiments depends primarily on coarsening kinetics. It is concluded that driving force for the coarsening is reduction of liquid-solid sur/ace area. Calculations based on two simple models show qualitative apreement with experinzent. 1 HERE has been considerable interest in recent years in determining effects of solidification variables on dendrite arm spacing in cast alloys. The interest has resulted primarily from the clear evidence that 1) the degree of homogeneity which can be obtained in a cast alloy with commercially practical homogeni- zation treatments depends on dendrite arm spacing, and 2) mechanical properties of the heat-treated casting depend on the homogeneity obtained.'-' In wrought alloys, microsegregation from the original ingot is carried to some extent into the final wrought product, and affects mechanical properties in similar fashion Experimental evidence available indicates that dendrite arm spacing in cast aluminum alloys is influenced only by cooling rate (or "local solidification timev*) and alloy content.Fig. 1, for example,

Jan 1, 1968

By E. P. Whelan

A recent investigation1 into the origin of "ghost boundaries" in dilute Cd-Mg alloys has indicated the persistence of a segregated solidification substructure in spite of a homogenizing treatment designed to remove such segregation. Although no grain growth experiments have been reported on these segregated alloys, the homogenizing treatment used in grain growth studies on other dilute alloys2-7 is similar in

Jan 1, 1968

By Robert M. Becker

A thick-wall cylinder solution applicable to the evaluation of anisotropic elastic parameters is derived for the interpretation of stress relief data. For a restricted class of problems, a special relationship among certain orthotropic moduli yields stress distributions for the plane orthotropic problem that are identical to the corresponding isotropic case. A ring or hollow cylinder with these specialized anisotropic properties subjected to uniform radial loads is one of the problems in this class. Consequently, known stress solutions are used to develop the strains and displacements for a specialized orthotropic thick-wall cylinder under uniform pressures. The results are consistent with anisotropic equations used in the evaluation of in situ rock stresses.

Jan 1, 1968

By J. C. Scully

In June, 1965, Sanderson and scully5 reported at the Conference on Environment Sensitive Mechanical Properties of Materials at the Research Institute for Advanced Studies at Baltimore that thin foils of titanium could be prepared by chemical polishing in a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. The technique is simpler than that since reported by Rice and Orava. As-received annealed titanium (containing 0.8 pct Fe and 30 ppm H) in the form of sheet 0.05 cm thick is placed in the solution and moved up and down. The reaction is violent but suitable foils are obtained very easily and consistently. A typical micrograph is shown in Fig. 3. The small precipitates were not identified. Yamane and ueda6 observed many spotlike features which they referred to as small dislocation loops. While their spots may be due to the reaction of the warm foil with the air as suggested by Rice and Orava, the precipitates in Fig. 3 are also found when foils of titanium are prepared by electro-polishing at low temperatures and subsequently examined in the electron microscope without any inter- mediate warming. Furthermore, they are not a surface effect. It is necessary to add that alloys of titanium cannot be so easily thinned by the chemical polishing solution described above since it contaminates the a, phase with hydrogen and produces y hydride. These matters are described at length in a paper7 and their relevance to stress corrosion is considered elsewhere.'-* Author's Reply The authors are grateful to Dr. Scully for bringing to our attention his hitherto unpublished technique for thinning unalloyed titanium, and deeply regret the unintended apparent duplication. The chemical thinning solution (7 parts HNO3 and 3 parts HF, by volume) reported by us is the same as that with which, for some period in the past, we had experienced success in the preparation of foils from single and polycrystalline niobium. Its subsequent effective application to titanium was a logical step, which, clearly independently of Scully, was conceived by Mr. Rice, to whom full credit is due. A few comments are warranted concerning some of the details of the preceding Discussion. It is evident to the discerning reader that the two thinning techniques under consideration are chemically almost identical, and in that sense are equally "simple". The chemical aspect is, of course, the one of primary importance in both communications. Thereafter, the relative simplicity is dictated by the mechanics of the actual thinning operation selected by the individual investigator. Our standard dimpling, or dishing, procedure was chosen with a view toward providing, for the electron transparent areas of the sample, the maximum protection from extraneous deformation during handling. That the long, straight dislocations visible in Scully's electron micrograph of a seemingly recovered structure closely resemble handling dislocations would tend to indicate the merit of our adopted technique. Features similar to those which Scully has attributed to precipitates, without any apparent diffraction contrast confirmation, were not observed in any of our clean foils taken from annealed or deformed specimens. This was admittedly somewhat surprising since the 3700 ppm (nominal) Fe in the A-70 commercial-grade titanium examined should have given rise to TiFe precipitates. Presumably these existed but were un-resolvable. Curiously, Scully's "precipitate1' density is fairly high although the iron content quoted was less than one-fourth of that in our material. One is forced to conclude from the evidence that prior thermal and mechanical treatments are responsible for the two different types of structure observed.

Jan 1, 1968

By Neil J. Sullivan, Goode. George E.

"The Adams mine, operated by Jones & Laughlin Mining Company, Ltd. and located near Kirkland Lake, Ontario, produces one million tons of iron ore pellets per year. This paper briefly describes the mining and concentrating operation and deals mainly with the operation of the pellet plant. The orebody consists of fine-grained magnetite and some hematite, with alternating layers of chert, and is mined by conventional open-pit methods. After crushing and grinding, the ore is concentrated by magnetic separation and flotation. Agglomeration is accomplished by the grate-kiln pelletizing process. The plant layout and general operation will be discussed in detail."

Jan 1, 1968

By J. H. Swisher

ALUMINUM deoxidation equilibrium in liquid iron has been the subject of many investigations. Sawamura and Sano1 have written a critical survey of the literature on this subject and consider the data of Gokcen and chipman2 and of d'Entremont, Guernsey, and Chip-man3 to be most reliable. The present study was undertaken to check these data and extend the range of the experiments to lower temperature. The experiments consisted of equilibrating 5-lb Fe-Al melts with recrystallized alumina crucibles at 1580o + 10oC, and analyzing the solidified ingots for aluminum and oxygen. The electrolytic iron stock contained 100 ppm C, 20 ppm 0, and trace amounts of other elements.* The stock was induction-melted in an atmosphere of 5 pet H2 in argon to attain equilibrium between the melt and the crucible. The temperature was measured with a W, 3 pet Re/W, 26 pet Re thermocouple, and the equilibration time was about 4 hr. The results are plotted in Fig. 1 along with curves obtained from the data of d'Entremont et al.,3 for temperatures of 1740o and 1910°C. The present results can be seen to be consistent with the previously reported high-temperature data. The reaction under study is AI2O3 (s) = 2 Al (l) +3O [1] for which the deoxidation product is Kl =[% Al]2 [%O]3 [2] (Under the experimental conditions, Fe A12O4 is not expected to form.4) In Fig. 2, values of log Ki evaluated at 0.01 pet A1 are plotted against 1/T, using data obtained from all the investigations under consideration. The deoxidation product is plotted in Fig. 2 in lieu of the equilibrium constant (normally obtained by evaluating Ki as pet A1 — 0) because of the uncertainty involved in extrapolating to zero concentration. The difficulty in extrapolating the present data for 1580°C is apparent curvature in the log Ki vs pet Al plot. This curvature is perhaps due to the uncertainty in oxygen analysis for concentrations of 5 ppm and below. For the data of Gokeen and chipman,' the extrapolation is also difficult because of experimental scatter. The line drawn through the points plotted in Fig. 2 may be represented by the equation:

Jan 1, 1968

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By John D. Ridge

Here are summarized 162 papers, published between 1933 and 1967, that deal with various aspects of ore genesis. Emphasis is placed on additions to, or modifications of, ore-formation theory, no matter what type of deposit is discussed. More space is given to papers on the formation of base-metal sulfides solely because more papers are written on this subject. The final conclusion is reached that a chemically and geologically sound theory for the genesis of ore deposits can be built around the concept of concentration of ore e’ements in a magmatically produced ore fluid and around such surface processes as may act to concentrate economically valuable materials from rocks of any origin exposed at the surface.

Jan 1, 1968

By Ted C. Briggs

Equations for the elastic pressure distortion of the volumes of a Burnett compressibility apparatus are developed and presented in this report for volumes under internal and external applied pressures. An experimental method for the determination of the external pressure distortion coefficients is presented. Young?s modulus and the internal-pressure distortion coefficients are computed from the experimentally determined external-pressure distortion coefficients. The temperature dependence of the pressure distortion coefficients and of Young's modulus is evaluated for the temperature range 0° to 80° C.

Jan 1, 1968

By Ronald P. Hollenbeck

Shales in the Appalachian Region of Kentucky and Tennessee were sampled and tested to determine their use as raw materials for the manufacture of lightweight aggregate by the rotary-kiln method. Nine samples were obtained from eastern Kentucky and 143 samples were obtained from eastern Tennessee. As a result of preliminary testing of these samples, two sources in eastern Kentucky and 11 sources in eastern Tennessee were resampled for rotary-kiln tests. The rotary-kiln tests showed the two sources in Kentucky and seven sources in Tennessee contained shale that would produce satisfactory aggregate. Lightweight aggregate processed from these nine sources was tested in concrete shapes and was found to be suitable for use in structural concrete.

Jan 1, 1968

By Shrikant Lele

INTRINSIC and extrinsic stacking faults may be formed in fcc structures by similar processes with bounding S-and D-Shockley partial dislocations respectively.' The only difference between these two dislocations is that the side on which the fault lies is reversed. The number of nearest and next nearest neighbors of atoms is identical for the two faults, but that of next next nearest neighbors is different. Thus, the energies associated with intrinsic and extrinsic faults may be expected to be different but of the same order of magnitude. An extrinsic fault can be constructed from two intrinsic faults on adjacent close-packed planes. This suggests that the extrinsic fault energy is higher than the intrinsic fault energy. It is, therefore, surprising that extrinsic faults have not been detected in X-ray studies2 of deformed alloys of low stacking fault energy. These have, however, been observed in cerium3 by X-ray diffractometry and in Au-4.8 at. pct Sn4 and Cu-16.6 at. pct A15 alloys by transmission electron microscopy.

Jan 1, 1968

Jan 1, 1968

By P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of' the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968

By H. Biloni

PORE formation during solidification has recently been studied theoretically by Piwonka and Flemings.1 For the ordinary conditions of cellular solidification, these authors state that there is a difficulty in explaining the formation of pores. The difficulty arises because the conditions necessary for pore formation are not those obtained during cellular growth. Therefore Piwonka and Flemings1 had to examine various unusual possibilities in order to explain the apparent presence of pores in a cellular substructure of aluminum, taken from Doherty.2 For aluminum, Doherty and Davis3 have developed a pitting technique to reveal substructure, which depends upon the condensation of vacancies from supersaturated solution after quenching. This technique as further developed4 was used to study solidification substructures. In the case of striations, delineation of the substructure is produced by the absence of surface pitting after quenching: in the vicinity of the striations the dislocations which constitute this substructure are sinks for vacancies. In the case of the cellular substructure the experimentally observed effect is the same. However, in this latter case Doherty and Davis4 suggested that micropores associated with the cellular substructure were the agent responsible for providing sinks for vacancies. This interpretation seemed necessary for the cellular substructure because no misorientation arising from a dislocation array could be observed. It is noted especially that Fig. 1 presented by Piwonka and Flemings1 and Fig. 5 by Doherty and Davis,4 as

Jan 1, 1968

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968

By G. Mempel, D. C. Yang, D. W. Fuerstenau

This paper describes details of the design and operation of a batch tumbling mill which has been used for a number of years in the laboratories at the University of California. In order that the energy expended for grinding can be measured accurately, this specially constructed laboratory mill has sensitive torque measuring apparatus. Torque measurements are given for a variety of conditions with this particular mill. In recent years, there have been numerous and fairly extensive investigations of grinding in tumbling mills reported in the literature. Most of these investigations have been carried out in mills with widely differing dimensions. As a result, comparison of results obtained from various investigations has been virtually impossible. If similar mills were used by different investigators, a considerable step forward would be taken in grinding research. A specially constructed laboratory mill with sensitive torque measuring apparatus has been used for a number of years in the laboratories of the University of California. The purpose of this paper is to describe details of the design and operation of this batch tumbling mill so that other researchers, who might be interested in obtaining data for intercomparison, could construct a similar device for their own research. Furthermore, since torque instrumentation is quite expensive, torque measurements are given for a variety of conditions with this particular mill so that those who may not wish to duplicate torque measuring apparatus can make reasonably accurate torque estimates merely by duplicating the loading conditions. It is not intended in this paper to present theoretical derivations of energy consumption in ball mills. This has been done e1sewhere.l-3 CONSTRUCTION OF THE MILL In order to eliminate rust problems with wet grinding, the mill and grinding media are made of stainless steel. The mill shell was rolled from 1/2-in. steel plate. The inside dimensions are 10-in. diam and 11-1/2-in. length, similar to the mill used by Charles.4 It is equipped with eight lifter bars (1/4-in. in height) whose dimensions are given in Fig. 1. The lifter bars have been bolted into the shell so they can be removed for experiments without lifter bars; however, all data presented here are for the mill with lifters. One end of the mill is fitted with two 1/2-in. diam removable plugs for filling the mill with liquid for wet grinding experiments. The mill is mounted on ball bearing rollers as can be seen in Fig. 2. The pillow block bearings are single-row self-aligning sealed ball bearings with 1-1/4 in. hole diam. The bearings supporting the mill shell are single row sealed ball bearings with

Jan 1, 1968

By N. E. Hanna

An investigation was made of pressure pulses produced by unconfined explosive blasts in underground openings. Four tests were made with TNT or modified amatol charges ranging in weight from 60 to 2,000 pounds; each test involved either single or multiple charges. Pressure-time profiles were obtained using mechanical self-recording pressure gages. The cube-root scaling law for peak pressure was found to be valid within about 1 tunnel diameter; at greater distances, the pressures obtained along direct paths were generally higher than this scaling law would indicate.

Jan 1, 1968

By G. L. F. Powell

TURNBULL and Cech1 reported undercooling small droplets (approximately 50 mp in diam) of a large number of metals by approximately 0.18 TE (TEoK = the equilibrium freezing point). This was considered to be the undercooling for homogeneous nucleation in

Jan 1, 1968

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1'761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant' used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.' The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*'1' of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968