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By Byron C. Hardinge, Michael Sokaski, Paul F. Sands, W. Loring III Mc Morris, David J. Akers

INTRODUCTION In the early days of coarse-coal cleaning by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken the loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Netherlands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War II in the laboratory of the Dutch State Mines under the direction of M. G. Driessen. A 15-tph (13.6 t/h) pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of Fuel in London.51 In April 1945, operation of this pilot plant was observed by H. F. Yancey, who was so impressed with the potential of the cyclone process that, on his return to the United States, a research program on the cyclone was immediately started by the US Bureau of Mines (USBM). This work led to an AIME paper in 1946 in which the first details of cyclone operation on American coals were made available.52 Commercial adoption of the cyclone proceeded in Europe, initially in the Netherlands, Germany, and France. In the United States, where coal is less costly and most of the coals are easy to clean and respond well to simpler cleaning processes, the first cyclone plant was not built until 1961.53 THEORY Before discussing the theory of a dense-medium cyclone, a brief description may be helpful to some readers who are not familiar with its basic operation. In a typical dense-medium cyclone, illustrated in Fig.7-51 a mixture of medium and raw coal enters tangentially near the top of the cylindrical section, thus forming a strong vortical flow. The refuse moves along the wall of the cyclone and is discharged through the underflow orifice. The washed coal moves toward the longitudinal axis of the cyclone and passes through the overflow orifice, or vortex finder, to the overflow chamber. Washed coal is discharged from this chamber, usually through a tangential outlet.

Jan 1, 1991

By Clément F. Bernier

One of the chief sources of the world's supply of asbestos lies in a belt of ultrabasic rocks which runs northeastward through an area called the Eastern Townships, south of the St. Lawrence River in the Province of Québec. The productive portion of this belt extends from the town of Asbestos in the south, for a distance of some 9,5 km to beyond the village of East-Broughton. The first discovery of asbestos in this region was made in 1874. Only crude fibre was produced until 1888 when the first mill was erected near the town of Black Lake. Since the inception of the industry, almost 100 years ago, no less than 100 different compa¬nies have been formed and 46 different mines have been operated. There are presently 5 active companies in the area providing direct employment for 4100 workers, down from 6000 during the seventies.

Jan 1, 1984

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By D. J. Mottern, F. Wald

SEVERAL systems have been investigated by Bates, Wald, and weinstein&apos; to determine the compatibility of pure PbTe with various metals. This was accomplished by experimentally determining the direction of the reaction given by Eq. [I]: The direction of this reaction is very important if alloys of the PbTe system are to be used in thermoelectric generators because the presence of free lead in the matrix, followed by incipient melting in the vicinity of the hot junction, could cause a bonding failure. According to anssen,&apos; the Au-Te system contains only one stable compound, AuTez. The initial alloy which was reacted was therefore of the composition AuTez + 2Pb. Ten-gram samples of PbTe plus 1, 10, 20, 30, 40, 50, and 70 at. pct Au were encapsulated in carbon-coated quartz capsules in vacuo. All materials were of semiconductor (99.999+ pct) purity. Carbon coating was used to prevent reaction of the quartz with any of the alloying constituents (the solubility of carbon in the constituents of the alloys is negligible). Each capsule was then placed in a thermal analysis furnace, melted, and cooled through the transformation region. Thermal arrests were monitored on a strip chart recorder. Each sample was subsequently examined microscopically after standard grinding and polishing techniques were applied. For better contrast between the phases, the samples were etched in Murakami&apos;s etch; however, both phases could be identified without etching. Several of the samples were ground into powder, stress-relieved, and X-rayed in a Debye-Scherrer camera using nickel-filtered Cu-Ka radiation. The phase diagram shown in Fig. 1 indicates that the pseudobinary system exists as a simple eutectic with no measurable (<I pct) solid solubility at either limit. Figs. 2,3, and 4 are photomicrographs of the structures obtained with 20, 40, and 50 at. pct Au, respectively. At higher concentrations of gold (>40 pct) slight divorcement of the eutectic occurred, apparently due to a) the difference in density between gold and PbTe (19.6 and 8.25 g per cu cm, respectively) or b) the nonideality of the liquid as noted by the curvature of the liquidus lines. The eutectic temperature was determined to be 742° ± 5°C. The composition of the eutectic was determined by extrapola-

Jan 1, 1969

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytic expressions were developed and applied in two preuious papers to predict effects of solidification variables on macrosegvegation. In this paper, experiments are reported to test the analyses quantitatively and qualitatively. Good quantitative agreement is obtained between predicted and measured compositions for the following types of segregation (all experiments were on laboratory-size ingots of Al-4.5 pct Cu alloy): (a) inuerse segregation, (b) composition distribution in ingots solidified with unidirectional heat and fluid flow, (c) simulated centerline segregation, and (d) segregation resulting fro, change in solidification cross section. In addition, qualitative agreement of prediction of theory with experiment is obtained for (a) segregation resulting from sudden change in heat extraction during solidification, (b) centerline segregation in a bidirectionally solidified ingot, and (c) under-riser positive segregation. IN two previous papers,&apos;&apos;2 it was shown that a variety of apparently different types of macrosegregation result from the same basic mechanism. This mechanism is the flow of solute -rich liquid to feed solidification and thermal contractions. Analytic expressions were derived and examples given of their application to predict macrosegregation. Calculations were for Al-4.5 pct Cu alloy. In this paper, we describe a series of experiments designed to test results of the foregoing calculations. All experiments were on laboratory-size ingots (weighing 10 lb or less), of A1-4.5 pct Cu alloy, nominal composition. APPARATUS AND PROCEDURE A typical mold and chilling arrangement used for unidirectional solidification is shown in Fig. 1. Before casting, this assembly was placed in an electrically heated air furnace, and heated to 680" to 700°C. When the plaster reached the desired temperature (usually 1 to 2 hr after the furnace temperature), the mold was filled through a funnel extending from the outside of the furnace into the cavity. The assembly, with liquid, was held for several minutes to allow convection to subside. The coolant, either air or water (depending on the desired solidification rate), was turned on and the ingot solidified. With the four sides and top insulated, heat removal for solidification was through the bottom surface, resulting in a fully columnar structure. Design of the casting cavity was varied, as discussed below, to produce desired macrosegregation effects. However, for castings solidified with unidirectional heat flow, the top was always open to the furnace atmosphere and temperature. The bottom sur- face rested on a chill through which the heat was extracted, and all other surfaces were insulated with plaster. In one case to be discussed, the mold design was changed to obtain bidirectional solidification. In this case, two vertical chills were used (on two faces of the mold) and the bottom was insulated. In a last case discussed, that dealing with under-riser segregation, experiments were conducted in bottom-chilled sand molds at ambient temperature. Except for this one case, all experiments were conducted in the electrically heated air furnace as described above. In many ingots, thermocouples were used to obtain continuous records of solidification. In all cases, these were chromel-alumel couples with output continuously monitored on a twelve-channel recorder. Where thermocouples were employed, these were embedded in the refractory mold walls during mold-making so their heads extended to the vertical centerline. Six to nine couples were employed, placed at intervals from the chill. METAL-MEL TING PROCEDURE Aim analysis was A1-4.5 pct Cu; alloy was prepared from high-purity aluminum (99.9 pct Al) and A1-Cu master alloy (50 pctOFHC Copper, 50 pct high-purity Al). The A1-4.5 pct Cu alloy was cast in 5- to 7-lb ingots for subsequent remelting for the macrosegregation experiments. Melting for ingot casting was as follows. After preheating the melting crucible for an hour or more, the charge was melted and superheated to a temperature of 690" to 720°C. After stirring, the melt was degassed with chlorine for 10 min. After stirring again for 1 min, a gas sample, under reduced pressure, was taken. When the sample was gas-free, the crucible

Jan 1, 1969

By Koichi Kashida, Mayumi Someno, Kazuhiro Goto

The present work has two objectives: first to develop an experimental method which would give some new information on the micromechanism of the reduction of oxides by gases at elevated temperature; second to clari,fy the intermediate phases of the W-0 system, formed during the reduction. A Galvanic cell with the solid electrolyte , ZrO2 . CaO, was imbedded in powders of W03, CuO, or Fe20s with two measuring electvodes and with a reference electrode. The change of the intraparticle gas composition was measured at An oxygen concentration cell consists of two electrodes separated by an electrolyte through which the transference of electrical charge is accomplished predominantly by the migration of oxygen ions. Many works have been reported on the oxygen con- 600" to loo@ C during the reduction by the gas mixture of hydrogen and argon. The intraparticle gas composition changes stepwise with time. The electromotive force of such temporary interruption corresponds to the equilibrium electromotive force of two solid phases formed during the reduction. The intermediate phases of W-0 system, which are formed in a large quantity during the reduction by hydrogen, are W0 2 W02.72 and WOz. The micromechanism of the reduction of oxides by gases is discussed. centration cells with the solid electrolyte of solid solution of zirconia and lime, since Kuikkola and wagnerl demonstrated the possibility of determination of standard free energy of formation of oxides by an electromotive-force method with the Galvanic cell. One of the present authors (K.G.) and his coworkers have applied the cells with the solid electrolyte of zirconia and lime to the following measurements:

Jan 1, 1969

By R. E. Smallman, I. Milne

The deformation behavior of single crystals of Nb-Mo alloys has been investigated with particular reference to the influence of composition, orientation, and temperature. Strong solid-solution hardening was observed reaching a maximum at the equiatomic cotrlposition and can be attributed to the difference in atomic size between niobium and molybdenutrz. Changes in the form of stress-strain curve, as shown by a high work-hardening rate and restricted elongation to fracture, were observed at a composition of Nb-85 pct Mo and are attributed to the presence of MozC DreciDitate. Conjugate slip was only extensive in dilute alloy samples; at the 50/50 composition deformation rnainly occurred by primary slip, and the onset of conjugate slip gave rise to failure by cleavage on (100). The variation of yield stress of Nb-50 pet Mo with orientation was consistent with slip on (011)(111) slip systems. The temperature deperndence of the yield stress between -196" and 250°C was similar to that of pure bcc metals, but at a much higher stress level; no evidence for twinning %as found. IN recent years the deformation behavior of various pure metals in groups VA and VIA has received considerable attention, but surprisingly little work has been carried out on binary alloys made by mixing metals from the two groups. Such an investigation would be of interest since single crystals of metals of group VA have been shown to deform characteristically with a multistage deformation curve1"3 while a parabolic type of deformation curve has been reported for most of the group VIA metals.4&apos;5 It has been suggested by Law ley and Gaigher~ that the difficulty encountered in obtaining multistage deformation curves for molybdenum in group VIA was possibly because of the presence of a microprecipitate of MozC which they observed even at carbon contents as low as 11 ppm. Recently a multistage deformation curve has been reported for molybdenum ," although the stages are not so definitive as those for group VA metals. The binary alloys of the particular refractory metals which have been investigated in single-crystal form include Ta-w,&apos; Ta- Mo,&apos; and Nb- Na." While a large amount of hardening was observed for alloys of the Ta-W and Ta-Mo systems, associated with room-temperature brittleness for alloys approaching the equiatomic composition, Ta-Nb remained ductile over the complete composition range with little or no solution hardening. Other systems have been investigated by hardness measurements on polycrystalline material and a discussion of the hardening of these alloys has been presented by ~udman." The purpose of the present investigation was to examine the deformation behavior of Nb-Mo alloys in detail, with particular reference to alloy composition and single-crystal orientation. In this way it was hoped to shed some light upon the restricted ductility of these alloy specimens. 1) EXPERIMENTAL PROCEDURE The starting materials were obtained in the form of beam-melted niobium rod and sintered molybdenum rod of suitable dimensions. Since niobium and molybdenum form a complete solid-solution series at all temperatures, alloy single crystals were produced by melting the two constituents together in an electron bombardment furnace (EBM). To produce specimens free from segregation a molten zone was passed over the length of each rod six times in alternate directions at a speed of 10 in. per hr. Typical specimens were analyzed for interstitial impurities by gas analysis and for metallic impurities by spectrographic analysis. The results of this analysis are shown in Table I. Many of the tensile specimens were also analyzed (after testing) by scanning the gage length in an electron beam microanalyzer, from which it was found possible to predict the approximate composition of a specimen from the original proportions of each element in the EBM. The tensile specimens were made with a gage length of 0.5 in. and diameter of 0.075 in., using a Servomet Spark machine. By careful machining on the finest range for the final i hr of this technique, surface cracks could be reduced to the level where they were easily removed by electropolishing in a solution of nitric and hydrofluoric acids. The specimens were strained at a rate of 10 4 sec-&apos; using friction grips designed to prevent accidental straining and maintain a good alignment before straining. The orientations of the individual specimens tested are shown in Fig. 1 and the corresponding compositions listed in Table I1 together with collated experimental data. 2)RESULTS a) General Deformation Behavior. The effect of composition on the room-temperature deformation curves of similarly oriented specimens is shown in Fig. 2. The yield stresses of the pure constituents, while not the lowest reported to date, were at least comparable with existing data. Although the solution hardening was large for alloys at either end of the phase diagram, and comparable with the Ta-W solution-hardening data of Ferris et a1.,8 the low work-hardening rate characteristic of niobium was sustained until a composition of Nb-85 pct MO had been reached. Associated with the peak yield stress ob-

Jan 1, 1969

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C&apos; where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.&apos;-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,&apos; and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.&apos; The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6&apos;14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke&apos; first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer&apos; who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier&apos; gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.&apos; The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown&apos; to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown&apos; has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler&apos; is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:&apos;

Jan 1, 1970

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of &apos;nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;&apos; this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By G. R. Belton, R. J. Fruehan

The Knudsen cell-mass spectrometer combimtion has been used to study the Fe-Al and Ag-Al liquid alloys. By application of the recently developed integration technique to the measured ion-current ratios, activities have been derived for the Fe-A1 system at 1600° C and for the Ag-Al system at 1340"C. The results are partially represented by the following equations: Internal consistency between the data on silver-rich and iron-rich alloys is demonstrated by application of the literature measurements on the distribution of aluminum between the nearly immiscible liquids iron and silver. The usual restrictions on the ratio of the mean free path of the escaping atoms to the orifice diameter of the Knudsen cell are shown not to be limiting in this technique. DESPITE the importance of a knowledge of the activity of aluminum in understanding deoxidation equilibria in molten steel, no direct studies have been made of activities in liquid Fe-A1 alloys at steel-making temperatures. Lower-temperature direct studies have, however, been carried out on aluminum-rich liquid alloys by Gross, Levi, Dewing, and Eilson&apos; at 1300°C and by Coskun and Elliott&apos; at 1315°C. Apart from phase diagram calculations by Pehlke, other determinations have been indirect and were made by measurement of the distribution of aluminum between iron and silver475 and combination of these data with extrapolated activities in the Ag-A1 system.~-% ecently, however, Woolley and Elliott have made a significant contribution by directly measuring heats of solution in the Fe-A1 system at 1600°C. The present authorslo have recently employed a Knudsen cell-mass spectrometer technique in a study of activities in iron-based liquid alloys. In this technique activities and heats of solution are determined from a series of measurements of the ratio of ion currents of the components; and since ion-current ratios are used, problems caused by changes in instrument sensitivity or cell geometry are overcome. Results obtained for the Fe-Ni system were found to be in excellent agreement with previous work, thus demonstrating the reliability of the method. The present paper describes a similar study of activities in the liquid Fe-A1 and Ag-A1 systems, this latter system being included in order that a meaningful comparison can be made with the above-mentioned indirect studies. INTEGRATION EQUATIONS A detailed derivation of the equations used to determine the thermodynamic properties from the measured ion current ratios has been given elsewhere;&apos;&apos; however it is useful to summarize them here. By the combination of the Gibbs-Duhem equation with the direct proportionality between ion-current ratios and partial pressure ratios, it was shown that for a binary system at constant temperature and pressure: where al is the activity of component 1 with pure substance as the standard state, N, is the atom fraction of component 2 in the solution, and I; and t&apos;2 are ion currents of given isotopes of the components. The activity coefficient is given by: this latter equation being more suitable for graphical integration. Combination of Eq. [l] with the Gibbs-Helmholtz equation gives an expression for the partial molar heat of mixing: EXPERIMENTAL A Bendix Time-of-Flight mass spectrometer model 12! fitted with a 107 ion source and a M-105-G-6 electron multiplier, was used to analyze the vapor effusing from the Knudsen cell. The arrangement of the Knudsen cell assembly was essentially that of the commercial instrument (Bendix model 1030) but with several modifications. Instead of heating with a single tungsten filament, a cylindrical tantalum-mesh heater was employed. Up to 1400°C simple resistance heating was used but above this temperature electron bombardment between the tantalum mesh and the tantalum cell susceptor was necessary. The temperature was measured by means of a Leeds and Northrup disappear ing-filament type optical pyrometer sighted on an essentially black-body hole in the side of the cell. Details of the temperature control, temperature measurement, and in situ calibration of the optical pyrometer can be found elsewhere.I0 In the investigation of the Fe-A1 system the Knudsen cells were constructed of thoria crucibles with fitted thoria lids (Zircoa). The cells employed in investigating the Ag-A1 alloys were made up of high-purity alumina crucibles (Morganite) with lids of recrystal-lized alumina (Lucalox). The cells were 0.370 in.

Jan 1, 1970

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

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

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult&apos;s law and obeyed Henry &apos;s law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner&apos;s interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.&apos; The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3&apos;) a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;&apos; hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.&apos; This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968