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By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.&apos; According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.&apos; In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By M. J. Marcinkowski, K. S. Sree Harsha

A detailed numerical analysis has been made of the equilibrium configuration of partial dislocations in a blocked deformation twin under an externally applied stress. Twins made up of both pure screw and pure edge partials have been considered. The components of stress in the vicinity of the twin tip associated with each of these configurations have been plotted. It has been found that at some critical degree of oblateness the shear stress fields of the blocked screw or edge twin can both sPontaneously nucleate slip, whereas only the component of stress oxx about the edge twin can nucleate and propagate cracks. TWINNING becomes a predominant mode of plastic deformation at low temperatures and/or high strain rates. Fig. l(a) shows what must be the first step in the formation of a deformation twin, namely the formation of a loop of imperfect dislocation bounding a stacking fault. In an fcc crystal the partial dislocations have Burgers vectors of the type 1/6 a,(112) and the fault is of the intrinsic type while in the bcc crystal the partials have Burgers vectors of the type ao(lll). The stacking sequence of (111) planes in a perfect fcc crystal is given by ABC ABC, and so forth, and in one which contains a twin by ABCABACBA, and so forth. It is apparent that the stacking fault and twin give rise to no mistakes associated with adjacent close-packed planes; however, with respect to second-neighbor close-packed planes the faulted crystal has twice as many mistakes as the twin. The energy of the twin boundary may thus be taken to be one-half that of the intrinsic fault boundary. In the case of the bcc crystal the stacking sequence of (112) planes is given by ABCDEFABCD, and so forth, in a perfect crystal, by ABCDCDEFA, and so forth, in a crystal which contains a fault, and by ABCDCBAF, and so forth, in one which contains a twin. An analysis similar to that applied in the fcc crystal shows that both the fault as well as the twin involve no neighbor violations across adjacent planes. However, there are twice as many violations across second-neighbor (112) planes associated with the fault as compared to that of the twin. Thus once again the energy of the twin boundary may be taken as one-half that of the fault. It is important to note that, unlike the fcc, the faults in the bcc crystal involve first nearest-neighbor violations and are thus expected to be of much higher energy than those in fcc crystals. A more detailed analysis of the material discussed above can be found in Ref. 1. To a good approximation then, the lenticular twin shown in Fig. l(b) can be generated by adding partial dislocation loops on successive (111) planes for fcc crystals or (112) planes for bcc crystals in the manner shown, with no additional expenditure of chemical energy other than that required for the fault shown in Fig. l(a). In practice, deformation twins are much more extended than that shown in Fig. l(b) and more closely resemble one shown schematically in Fig. l(c). It is readily apparent that the free energy of the twin and matrix are identical. In those cases where the partials lead to a structural change, the free energy of the material contained within the dislocation array is lower than that of the matrix and we have the so-called martensite transformation. The present investigation is the first in a series of five major theoretical-experimental efforts which will deal with the static and dynamic behavior of twin nucleation and growth. There has been a recent surge in activity pertaining to the equilibrium shapes of twin lamellae2&apos;3 and

Jan 1, 1969

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts&apos; technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts&apos; technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

By Pierre I. Desré, Donald T. Hawkins, Ralph Hultgren

The torsion effusion method has been used to measure the vapor pressure of thallium over pure thallium in the temperature range 931" to 996&apos;k The resulting 100 cal per g-atom is in excellent agreement with previous values. Vapor pressures of T1 above seven Ag-Tl alloys ranging from 33 to 90 at. pct T1 were measured at 979K. Calculated silver activities show a positive deviation from Raoult&apos;s law, approaching ideality near the liquidus. Measured thallium activities scatter less than previous measurements using the electromotive force technique. Values for the silver component were calculated by Gibbs-Duhem integration. This paper reports the results of a study of the liquid Ag-T1 system by the torsion effusion method. The method has been discussed in detail previously1 and will be only briefly summarized here. The sample is contained in a cell which is suspended on a torsion wire. Vapors effusing from orifices on opposite sides of the cell exert a torque on the wire. The torque is related to the vapor pressure by the following relation: where D is the torsion constant of the wire, 4 the angle of torque, fl and f2 the correction factors determined by Freeman and seamy2 to account for orifice length, a1 and a2 the areas of the orifices, and ql and q2 the distances of the orifices from the axis of rotation. By using the same cell for pure thallium and the alloy, it follows that: so that most systematic errors are eliminated in determining the activities. EXPERIMENTAL 99.999+ pct T1 was obtained from the American Smelting and Refining Co. and 99.999 pct Ag was obtained from Cominco American, Inc. Seven Ag-T1 alloys, ranging in composition from x^\ = 0.33 to 0.90, were prepared by melting together weighed amounts of the pure metals in sealed, evacuated Vycor tubes and quenching the melts in water. The apparatus and graphite cells were the same as those used by Hawkins and Hultgren3 in their study of the Pb-Sn system. RESULTS Ten measurements were made on pure thallium in the temperature range 931" to 996K, and the results are presented in Table I. Values of were calculated using tabulated Gibbs (free) energy functions.4 No dependence of on temperature or orifice size was found, indicating that equilibrium was attained. Data for the Ag-T1 alloys are shown in Table 11. Values were smoothed with respect to composition by a plot of where . DISCUSSION The value = 43,520 * 100 cal per g-atom for pure thallium (95 pct uncertainty limit) is in excellent agreement with previous investigations.4 In the Ag-T1 system, this study shows positive deviations from Raoult&apos;s law at all compositions. Fig. l gives the phase diagram according to Hansen, and Fig. 2 presents the activity values measured in this study as well as those from electromotive force measurements at 950°K by Terpilowski, Kundys, and slaby.&apos;

Jan 1, 1969

By N. Standish

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

Jan 1, 1969

By W. R. Wilcox

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

Jan 1, 1970

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

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

Jan 1, 1970

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,&apos;&apos; indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.&apos;&apos; The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15&apos;16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author&apos;s Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener&apos;s equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;&apos;-&apos; and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te&apos; forms on cooling at 829°K by a peritectic reaction.&apos; Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l&apos;&apos; It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~&apos;~ The heats of formation of InSb at 78", 273&apos;, 298", and 723°K have been measured5-&apos; and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult&apos;s law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of &apos;TiCr, is —0.76&apos; lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,&apos; no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,&apos; regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal&apos; was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult&apos;s law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to &apos;martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,&apos;-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.&apos; The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,&apos; a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By D. A. Koss, R. O. Gordon

Changes in the ultrasonic attenuation in steel specimens have been observed during tensile tests. Samples of AISI 1020, 1045, and 1095 steel quenched and tempered to a spheroidized condition have been used. Both attenuation and microstrain measurements fail to reveal preyield dislocation motion in the as-tempered specimens. Upon reapplication of the load to samples in the strain-aged condition there is a large preyield attenuation increase but no observable micvostrain up to 90 pct of the flow stress. These and other observed changes can be related to changes in the free disloca-tion density and the average dislocation segment length. The results show that the increase inflow stress in the strain-aged condition is caused by increased fric-tional stresses rather than by dislocation pinning. Strain aging is found to proceed through three distinct stages. The second of these follows the t2,3 law and is characterized by an activation energy of 20 kcal per mole. RECENT years have seen substantial progress in the understanding of the sharp yield-point phenomenon in metals; the influence of solute atom pinning of dislocations, of dislocation multiplication, and of the stress dependence of dislocation velocity on the stress-strain curve has been investigated. Evaluation of the relative importance of these factors in the various metals and alloys is not complete, however, because observation of the stress-strain curve alone is not sufficient to determine the yield mechanism. In the experimental study of the sharp yield point it would be desirable to be able to directly observe the dislocations in a bulk specimen. Ideally, the observations should be made during deformation because of the rapidity of recovery processes in lightly strained metals. While direct observation of dislocations under these conditions is not possible, certain physical properties sensitive to the dislocation structure can be observed while a test specimen is undergoing deformation. Of these properties, one of the most useful is the ultrasonic attenuation. The total observed attenuation, a, is due to a number of causes: acoustic diffraction, scattering by inhomogeneities in the structure, heat flow, magnetostriction, and dislocation damping. Satisfactory measurements of the absolute a are difficult to make because all of these factors cannot be evaluated in any given specimen, but changes in a due to changes in the dislocation contribution alone can be reliably observed by appropriate technique. Because dislocation damping is sensitive to small concentrations of long, free dislocation segments, observation of acoustic attenuation due to dislocations is particularly useful in the study of the early stages of plastic deformation. In the experiments to be described, acoustic-attenuation measurements have been made on steel samples as these were pulled through their yield in tension. While many details of dislocation-damping phenomena in the bee metals remain obscure, the main characteristics of this type of internal friction are established. At low strain amplitudes and at frequencies well below that of dislocation resonance (the conditions of these experiments) the dislocation contribution to a is given by1 where A is the density of freely oscillating dislocation segments, L is the average segment length, B is the damping constant for a moving dislocation, w is the frequency, O is an orientation factor, C is the dislocation line tension, and t is a numerical factor relating average segment length to the distribution of lengths. Because of its fourth-power dependence on L, a is highly sensitive to changes in dislocation free segment length such as might arise from unpinning, recovery, jog formation, or dislocation intersection. The above equation is not valid near the resonant frequency of dislocations, but the segment length in steel is believed to be much too short to cause over-damped resonance near 10 Mc; this will be discussed later. In the present experiments plastic-strain measurements with a sensitivity of 2 x 10-5 were also made during the early stages of loading in order to detect preyield strain. The general plan of the experiments is to observe

Jan 1, 1967

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

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967