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By Hsun Hu, R. S. Cline

The annealing behavior and the mechanism of re-orientation during recrystallization of iodide titanium cold-rolled 94 pct have been studied in detail. Results indicate that recrystallization occurs by the nucleation and growth of new grains, as in other common metals. Recrystallization nuclei form by the coalescence of subgraim, and the change in texture as a result of recrystallization is largely due to selective growth among the nuclei formed. The annealing of titanium is characterized by a wide range of overlap of the various stages of the annealing process, which may be responsible for a range of activation energies observed, and for the apparently gradual change in the annealing texture as a function of time or temperature. The deformation and recrystallization characteristics of titanium and zirconium are very similar. In cold-rolled strip, the deformation texture consists of two symmetrically oriented components, each having the basal plane laterally tilted at about 30 deg from the rolling plane and the [1010] direction parallel to the rolling direction. Upon annealing for recrystallization, the change in texture can be described, for simplicity,* as rotations around [0001].2'6'8 According to McGeary and Lustman,' recrystallization occurs in zirconium through normal growth of the subgrains, which they called "domains", without the nucleation of new grains; and the magnitude of rotation around the [0001] axis increases gradually during the progress of recrystallization. If these conclusions were true, the mechanism of recrystallization in zirconium would be basically different from that in most metals, since it is commonly known that recrystallization with reori-entation always involves the migration of high-angle boundaries. In an attempt to clarify the situation, the mechanism of reorientation during recrystallization in iodide titanium cold-rolled 94 pct was studied in detail. The structural and textural changes upon annealing at various temperatures were examined by optical and transmission-electron microscopy, X-ray pole figures, pole density distribution measurements, and micro-beam techniques. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. An iodide titanium crystal bar was are-melted and solidified in a cold-hearth crucible under a purified argon atmosphere. The solidified ingot had dimensions of approximately 3 by 1/2 by 3 in. One face of the ingot was somewhat uneven, but was as clean and shiny as the remaining parts of the ingot. Large grains with a Widmanstatten internal structure were clearly shown on the shiny surfaces, indicating the occurrence of P — a transformation upon rapid cooling from the melt. Analysis of the are-melted ingot indicated C 0.033, N 0.010, H 0.013, 0 0.002 in weight percent, and traces of iron, copper, and silicon as detectable impurities. The ingot was cold-rolled -40 pct to 0.300 in. thick with a reduction of 0.005 in. per pass. The defects on the uneven side of the ingot were then removed by machining. This reduced the thickness to 0.285 in. The piece was then recrystallized by annealing at 800°C for 1 hr in a fused silica boat charged into a fused silica tube furnace under a vacuum of 10~5 mm Hg. To refine the grain size, the recrystallized metal was again cold-rolled 40 pct to 0.170 in., then annealed at 700°C for 1 hr. These treatments yielded a strip with a uniform equiaxed grain structure, having a penultimate average grain diameter of 0.04 mm and a hardness of approximately 90 Dph. Final rolling reduced the thickness from 0.170 to 0.010 in., corresponding to a reduction of 94 pct. The strip was rolled in both directions by reversing end for end between passes. Surface lubrication was provided by oil-soaked pads attached to both rolls. Specimens of 1 in. length (for X-ray examinations) and +in. length (for hardness and microstructure examinations) were cut from the rolled strip, and a width of & in. was cut from the edges of each specimen by a jeweler's saw. These specimens were then etched in a solution of 10 cu cm HN03, 5 cu cm HF, and 50 cu cm H,O to 0.008 in. thick to remove the surface metal, as well as the distorted metal at the saw cuts, prior to annealing or measurements. To minimize any surface reaction with the atmosphere, all specimens were kept in an evacuated desiccator. Isothermal Anneals. All annealing treatments were conducted in vacuum in a fused silica tube furnace as described earlier. The temperature of the furnace was controlled to within *2"C. The specimen was placed in a fused silica boat, then pushed into the hot zone of the furnace. It took about 5 to 6 min for the specimen to reach the furnace temperature. After the specimen was held at temperature for a desired length of time the boat was pulled to the cold zone of the furnace; the heating-up period was excluded from the isothermal annealing time. Thus, the uncertainty in annealing time is higher for very short anneals, but negligible for long anneals.

Jan 1, 1969

By J. Steininger

The Hallimond tube flotation of sphalerite and pyrite with sulfhydryl collectors has been found to be inhibited near neutral pH in the presence of copper salts. Alkalimetric titration studies of the reactions between collector and activator indicate that this effect is apparently related to the formation of basic copper collector complexes. The conditions of formation of these compounds and their stability are in good agreement with the depression observed in flotation experiments. The general procedure employed in the flotation of zinc sulfide minerals requires activation of the mineral surface by heavy metal ions, usually copper, which react more easily than zinc with the common short-chain ionic sulfhydryl collectors.' Commercially, zinc flotation is carried out under alkaline conditions (pH 7 to 10.5), but small-scale experiments indicate that zinc sulfide minerals can also be activated and collected under acid conditions. Selectivity, however, becomes poor at low pH and undesirable materials such as pyrite, silicates and carbonates tend to report in the float. Several years ago, Wark and Sutherland~, measured the contact angles of air bubbles on copper-activated sphalerite immersed in various sulfhydryl collector solutions. When represented, as in Fig. 1, on pH-sodium cyanide diagrams, the results are characterized by 'islands' of non-contact near neutral pH and

Jan 1, 1969

Jan 1, 1969

THE increased demand for titanium alloys with improved high-temperature creep strengths has stimulated interest in silicon as an alloying addition to titanium. Silicon is a potent solid-solution strength-ener and, if added in sufficient concentration and properly heat-treated, can also dispersion-strengthen titanium by eutectoid decomposition.' However, better understanding of the nature and distribution of the resulting silicide dispersion in more highly alloyed titanium matrices is necessary for the development of useful titanium alloys which utilize the latter strengthening mechanism. This note describes the chemical and crystallographic characteristics of the silicide phase as it occurs in a typical high-temperature near-a titanium alloy matrix. Several Ti-6A1-3Sn-3Zr a11oys containing various amounts of silicon ranging from 0.1 to 1.0 pct were melted as 10- to 20-lb ingots and processed into 1/2-in.-diam bar stock. The microstructures of specimens annealed at various temperatures were conveniently summarized by the (Ti-6Al-3Sn-3Zr)-Si pseudobinary phase diagram illustrated in Fig. 1. Comparison with the Ti-Si equilibrium diagram indicates the substitutional solutes (Al-Sn-Zr) increase the eutectoid temperature and decrease the a terminal solubility. Annealing at temperatures sufficiently high to dissolve the silicon in a ß solid solution and cooling rapidly enough to preclude coarsening generally produced a uniform dispersion of fine silicide particles, whereas annealing at temperatures near but below the ß transus produced relatively coarse silicide particles. Annealing in the limited a, plus 3 region produced a duplex coarse and fine silicide array. Several a-annealed specimens were examined by X-ray diffraction to determine the crystallographic identity of the precipitate phase. Copper Ka X-ray diffraction patterns of bulk specimens which contained 0.5 and 0.8 pct Si were virtually identical to that of the silicon-free Ti-6Al-3Sn-3Zr base alloy except for a slight shift in some of the high-angle diffraction lines. Apparently the silicide volume fraction was too low to be detected in bulk specimens. X-

Jan 1, 1969

By S. J. Aparo

Phosphate mining and beneficiation in the State of Florida are presently being carried on by 12 different mining companies with a total of 21 mining and flotation plant locations. Their combined production of both washer rock and flotation concentrate was approximately 28,000,000 long tons in 1968. This accounted for 70-72% of the total U. S. production and close to 30% of the world's output of this mineral. From this extensive activity in the Florida phosphate field, one basic flow sheet for beneficiation of the ore has developed over the years as the most commonly employed. In fact, all of these plants with the exception of two beneficiate Florida pebble phosphate using a basic operation as illustrated in Figure I. The two plants which differ from this general approach are not using raw matrix as feed. In one instance, +14 mesh pebble is ground in a rod mill to release free silica which is subsequently removed in a cationic froth flotation circuit using an amine acetate blend and kerosene. This technique generally results in a 4-7 BPL unit upgrading of the feed pebble. The other exception to the standard flow sheet illustrated in Figure I is an operation which is beneficiating tailing piles. In this case, the material is first subjected to cationic froth flotation in order to upgrade the feed to a point comparable to normal matrix. Thereafter, after, the phosphate is floated in an anionic rougher circuit followed by cationic flotation of the silica in a cleaner circuit.

Jan 1, 1969

By Robert H. Holgers

Eveleth Taconite Co. was chartered on July 29, 1963, and is 85% owned by Ford Motor Co. and 15% by Oglebay Norton Co. The latter also serves as managing agent. The location of the company's facilities is depicted in Fig. 1. The Thunderbird mine is located midway between the cities of Eveleth and Virginia, Minn. (Fig. 2). The Fairlane plant and General Office are located approximately 10 miles south on the St. Louis River near the community of Forbes (Figs. 3 and 4). The crude ore and the finished pellets are transported by a common carrier railroad, the Duluth, Missabe & Iron Range Railway Co. The facilities are also serviced by the Duluth, Winnipeg & Pacific Railway Co. Pellets are hauled year around by the DM&IR to its docks 60 miles south in Duluth, Minn. Ford Motor Co. consumes its share of the high grade pellets at its Rouge plant in Dearborn, Mich., and Oglebay Norton Co. sells its share in the open market. HISTORY Following six months of preliminary engineering by the initial staff of Eveleth Taconite Co. and the Western Knapp Engineering Div. of Arthur G. McKee & Co., the project was approved by Eveleth's board of directors on Apr. 17, 1964. On May 1, 1964, contracts were awarded to McKee for the mine, coarse and fine crushing and concentrating facilities, and to Allis-Chalmer for the pelletizing facilities. The pre-production surface overburden stripping contract was awarded to Skubic Brothers Co., Virginia, Minn. Ground-breaking ceremonies were held at the Thunderbird mine on

Jan 1, 1969

By Robert R. French

Beneficiation of low-grade nonmetalliferous mineral deposits by electronic color sorting is currently undergoing a period of rapid development. For those deposits in which the specific gravity, strength, soundness, and electric and magnetic properties of the ore and gangue are similar, the possibility of separation by color, reflectivity, or fluorescence offers hope for the utilization of much poorer quality ore than previously thought possible. For those ores in which consistency of color is required or for which a dry process is preferred, the electronic color sorter is particularly adaptable. Tests performed late in 1966 and reported herein are the result of continued interest in the dry beneficiation of gypsum and the development of higher capacity color-sorting machines. These tests should be considered only as an indication of the efficiency of the process and only with respect to the low-grade, untreated ore tested. Although most of the ore mined in Martin County, Ind., is of acceptable quality, a few thin carbonate strata and irregular nodules of dolomite and limestone are present within the main evaporite bed (Fig. 1).

Jan 1, 1969

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By Arthur M. Ribe

In my experience, nothing helps me better to get off to a good start in preparing a paper or a talk than a copious consultation with a comprehensive dictionary. I also feel defining the perimeters of a particular subject is helpful to the listener and reader. Sometimes thus precisely defining even the most common of words is helpful. Our general topic this morning as all of you know is "Transportation of Industrial Minerals." The definition of transportation given by the dictionary which I think is appropriate here is: "Systems and modes of conveyance of persons or goods from place to place." Our preceding panelists have outlined for you the state of the art inso¬far as systems and modes of conveyance from place to place are concerned today via rail, water and motor. My assignment is somewhat different as indicated by my topic, "The Traffic Manager in an Industrial Minerals Operation."

Jan 1, 1969

"Accelerated expansion of Western Canada's metallurgical coal industry has again stimulated considerable exploration activity in the Rocky Mountain Foothills Belt and influenced much of the R&D related to transportation, processing and carbonization. Preparation R&D has included further pilot-plant work on desulphurization, spherical agglomeration and modified compound cyclones (which are also proving themselves in other mineral beneficiation studies). Combustion research, aside from increasingly stressing control of combustion source pollution, has directed special attention to lignite PF firing and problems arising from lignite ash. Studies directed toward the non-fuel utilization of coal have centered on such diverse topics as active carbons, carbonaceous filter media, plant nutrients and industrial applications of humic acid derivatives. In addition, a number of long-range research projects related to such matters as coal chemistry and pyrolysis have been actively pursued, and further attention has been given to improved sampling techniques and analytical methods."

Jan 1, 1969

By G. R. Webber, L. M. Azzaria

"The wide interest in the application of the geochemistry of mercury to mineral exploration is leading to the continued development of a variety of analytical methods for the determination of nanogram quantities of this element. The various methods have different degrees of reliability, sophistication and portability. In this investigation, two simple portable instruments were used in geochemical prospecting surveys -an ultra-violet absorption instrument and a similar one modified with gold for the removal of interfering substances. The results show the application of the method to the determination of mercury in soils of different organic content, and in rocks, sulphides and air."

Jan 1, 1969

In conjunction with a study on wear of drag bits the effect of clearance angle on penetration rate was studied.Increases in clearance angle from 24 1/2 up to 30° gave an increase in penetration rate. Thereafter the rate was apparently affected by partial clogging with cuttings.Analysis of results was by a linear regression model and the t-test was applied to assess the significance of parameters in the penetration equation.

Jan 1, 1969

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By A. J. Stapleton

"This paper gives a brief description of the occurrence and development of the Needle Mountain mine at Gaspe Copper Mines, Limited and describes the trackless mining equipment used in this highly mechanized underground operation.Maintenance of the trackless equipment is considered in detail, with particular emphasis on scheduling and control, examination and inspection. All maintenance is carried out in an underground garage, and the facilities for maintenance and field repairs are also described. Maintenance costs are given for various units and the figures for different types of loading and haulage units are compared to support the trend toward larger units and the increasing use of rubber-tired loaders."

Jan 1, 1969

By W. J. D. Stone

"For several years, the existence of a deposit of barite (BaS04) near Brookfield, Nova Scotia, has been known. A very large deposit of strontium (SrS04) near Sydney, Cape Breton, is a more recent discovery. Cape Chemical Syndicate has been formed to work the deposits. A five-million-dollar integrated mineral processing and chemical plant is planned for Sydney to produce various compounds of barium and strontium. The mineral processing plant includes the Jones Wet Magnetic Separator and will produce high-purity barite and celestite. These products will be processed further in the fine grinding plant and the chemical plant. The general project is described, covering the deposits, processing and markets."

Jan 1, 1969

Jan 1, 1969

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

By Robert Stefanko

The concept of disposing of liquid industrial wastes by deep-well injection is not a new one. Brines associated with crude oil long have been disposed of in this manner, with the additional benefit of aiding secondary oil recovery. More recently, with the expansion of nuclear energy, the lethal, highly radioactive wastes which are by-products of the fission process have created severe disposal problems. During the past ten years, a variety of industries have resorted to subsurface disposal, some of the details of which are given elsewhere (1,2). The list reveals wide variations in injection rate, pumping pressure, cost, and waste disposition. Included are successful installations in Western Pennsylvania.

Jan 1, 1969

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin' in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.' The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.' Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969