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By Persifor Frazer

I DESIRE to say that, owing to the number of papers which have been more or less crowded at this session of the Institute, and the fact that, as one of the Local Committee, I have the distinguished honor to feel somewhat like one of the hosts, I should not tax the patience of members at this late hour, but would have my paper read by title were it in any way possible to do this. But the task I have set myself this evening is to present to the eyes of the members of the Institute certain objects which have occupied more or less of my time during the last eighteen months or two years. The objects I allude to are some of the igneous rocks of this country, which, until quite recently, have been less understood than any others. It will be well known to some of the members that some of the cooled lavas of a previous age of our planet, when not directly coarsely crystalline and granular, were considered and spoken of as " natural glasses," or perfectly uncrystalline, vitreous, or hyaline masses of matter. Among the first results of the use of the microscope was the dispersion of this fallacy. Sir David Brewster, Mr. H. C. Sorby, and William Nichol (the discoverer of the celebrated calcite prism, which bears his name), had, with greater or less success, examined sections of various rocks and minerals, both by transmitted and reflected light, and also in the form of powder. But, until the genius of Vogelsang undertook the subject, these investigations had no permanent value, nor did they constitute an independent line of mineralogical and geological research. Since the close of his labors, by Vogelgang's premature and much-lamented death, the subject has been made one of renewed interest by his brother-in-law, Ferdinand Zirkel, as well as by Rosenbusch, Tschermak, and many others abroad, and at home by the commencement of a systematic study of the traps of Connecticut by Messrs. E. D. Dana and G. W. Hawes, of New Haven, and by the splendid set of described sections of the traps of the West which have been furnished by Zirkel to illustrate Clarence King's report. I had the honor of presenting a large number of thin sections of our traps at the Washington meeting, for the inspection of the mem¬bers, with the aid of a table microscope belonging to the Smithsonian Institution. Here I propose to project these sections upon the

Jan 1, 1877

By R. F. Mehl, G. T. Horne

Diffusion coefficients and mobilities were determined as functions of concentration in the a phase of the Cu-Zn system. Use was mode of incremental diffusion couples to determine the Kirkendall effect at various concentrations. Darken's analysis was used to calculate the individual diffusion coefficients and mobilities from these data. The general diffusion coefficient is a single-valued function of the concentration in this system to within the limits of accuracy of the experimental methods used. The form of the various functions (diffusion coefficients and mobilities) of concentration is the same in every case: it is essentially the same as the usual D vs c curve. AS Darken' has pointed out, the knowledge that the movements of different atoms diffusing in the same lattice need not proceed at the same rate is old. Ionic lattices are the classical examples; application of the generalization to lattices with metallic bonding was much more slowly accepted. It remained for Kirkendall'' to show clearly that metallic diffusion need not be symmetrical with respect to both species. Several investigators" have confirmed the initial observation of a "Kirkendall effect:" marker movement accompanying diffusion. They have extended it to other systems and conditions. The theoretical interpretations have been many; ne of the first and simplest of these is that of Darken"' which is essentially mechanism independent. Darken has shown that the Kirkendall experiment permlts a calculation of the individual diffusion coefficients and, coupled with activity data, offers a means of measuring the mobilities of the separateatoms in a binary diffusion process. There is no published information on the effects of concentration and temperature on the individual diffusion coefficients or on the mobility values in binary solid solution; this paper provides such information for zinc and copper in a brass. For purposes of clarity, the overall D value obtained, for example, from the Boltzmann-Matano solution to Fick's law, will be designated as the "general diffusion coefficient;" and the diffusion co- efficients for the separate diffusing species will be designated as the "individual diffusion coefficients." Experimental Procedure The authors have accepted Darken's analysis and have measured mobilities on this basis. The findings of da Silva and Mehl are accepted: that the Matano interface, defined as the origin of coordinates for the Boltzmann-Matano solution to Fick's law, coincides with the original weld interface; that the "shift" of a marker is the distance between the Matano interface and the marker; that the observed porosity is too small sensibly to affect this result; and that the shift is a linear function of the Matano area, the area defined as the absolute magnitude of the area on either side of the Matano interface. Alloys: The a-phase of the Cu-Zn system was chosen for investigation. The measurements were made on incremental couples for two separate reasons: l—it has been questioned whether D, the general diffusion coefficient, is a single-valued function of concentration (a comparison of the D-values for couples with small concentration range, e.g., 10 vs 20 pct Zn, against those from a wide concentration range, e.g., 0 vs 30 pct Zn, will answer that question); and 2—on the Darken analysis, the mobility can be determined only at the concentration at which the marker is observed to lie (this is but one concentration in a single couple) but choosing a series of incremental couples in the range between 0 and 30 pct Zn provides mobility values at several concentrations, thus giving mobility as a function of concentration. Four alloys were chosen; nominally, pure copper, copper with 10 pct Zn, copper with 20 pct Zn, and copper with 30 pct Zn. This allowed six different types of diffusion couples to be prepared, promising mobility determinations at six different concentrations, but having a minimum range of 10 pct Zn. The copper was an especially prepared pure copper supplied through the courtesy of the Ameri-

Jan 1, 1956

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of' the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak's theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967

By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,' has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers' measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett's measurements on lithium indicated an angle of 3". According to the Burgers' mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers' mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard&apos; has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn&apos; who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99&apos; pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954

By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

The effect of such variables as feed size, particle shape, cleavage, and hardness on the relative proportion of impact, abrasion, and chipping events in a tumbling mill is demonstrated. The concept of an average event, which is a combination of the three comminution mechanisms, is introduced. It is postulated that the average event in a particular mill determines not only the size distribution but also the energy-size reduction relationship for the comminution process. Fragmentation of particles in tumbling mills appears to result from a combination of impact, abrasion, and chipping grinding.&apos; The relative rates of size reduction attributable to any of the basic grinding mechanisms must depend upon a number of variables, such as feed size, particle shape, hardness, and the number and kind of particles in the mill. The purpose of this paper is to show experimentally how these variables in the properties of materials affect the size distributions obtained by grinding the material&apos;s in a laboratory tumbling mill. The resulting size distributions will be intetpreted in terms of a combination of three comminution mechanisms. METHODS AND MATERIALS In this study, minerals of widely differing properties were ground either separately or as mixtures in laboratory mills using rods or balls for grinding media. The materials used include quartz, Tuolomne, limestone (99.8% CaCO3), barite, corundum, galena, pyrite, glass beads, and crushed glass. The mill used was 8 in. in diam. and 9-1/4 in. long. For the ball milling tests, 17.6 kg of steel balls (36: 7/8 in. balls, 178: 1 in. balls, and 44: 1-1/8 to 1-1/4 in. balls) were used. For the rod milling experiments, 17.6 kg of steel rods 9-1/16 in. long (25: 5/8 in., 10: 3/4 in., and 5: 7/8 in. in diam.) were used. In each test, 1 kg of solids were ground wet at 60% solids at 77 rpm. In all cases except where otherwise specified, the feed to the mill was 4 x 8 mesh material. Size distributions of the ground products were determined by a wet-dry sieving procedure with Tyler series sieves. Size distributions of mixed products containing limestone were determined by dissolving the limestone with acid and sizing the residue. EXPERIMENTAL RESULTS AND DISCUSSION If the size distribution of the product from a tumbling mill depends upon the relative proportion of impact and attrition (abrasion and chipping) events, altering the grinding conditions may change these proportions and consequently alter the size distribution of the product. Data to illustrate this point can be taken from Gaudin&apos;s classic 1926 paper.2 In one series of experiments, Gaudin ground quartz of different initial sizes for four hours in a laboratory ball mill with 7/8-in. balls. In Fig. 1, his data are reproduced as the cumulative fraction finer than the stated size for the following initial feed sizes: 13.3 x 9.4 mm, 6.7 x 4.7 mm, 2.6 x 1.6 mm, and 0.83 x 0.59 mm. As the feed size was decreased, a dramatic change in the shape of the size distribution curves took place, even though the amount of minus 100-mesh

Jan 1, 1964

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By Charles A. Anderson

The Bagdad copper deposit is of the disseminated type (porphyry copper) occurring in a quartz monzonite stock of late Cretaceous or early Tertiary age. This stock, located essentially at the intersection of two dike swarms, is the only one of several stocks cropping out in the area which is appreciably fractured and mineralized. Most of the rocks in the area are of pre-Cambrian age, but their structures have had no discernible influence on the copper mineralization. Hypogene alteration of the quartz monzonite includes the addition of quartz, orthoclase, and sericite and recrystalli-zation of biotite. The hypogene sulphides are pyrite, chalcopyrite, and molybdenite, the latter younger than the chalcopyrite. The late Cretaceous or early Tertiary igneous rocks, veins, and faults were controlled by northeast and northwest shear zones, the intersection of which marks the zone of appreciable copper mineralization. The minor mineralized fractures carrying the bulk of the copper have a preferred orientation parallel to the intersecting shears, and it is concluded that they are of tectonic origin rather than the result of shrinkage on cooling, crystallization, or mineralization. Supergene enrichment during late Tertiary or early Pleistocene time formed a chalcocite zone providing the minable copper ore. The enrichment was controlled in large part by northeast and northwest faults, prticularly at their intersection or where the faults are closely spaced. Introduction A major objective in a regional geologic study of a mining district is to determine whether any structural pattern can be found that has a bearing on the control of mineralization. The Bagdad copper deposit is of the disseminated type (porphyry copper) occurring in a.quartz monzonite stock which is located essentially at the intersection of two dike swarms (Fig 2). Of several quartz monzonite stocks in the area only this One is appreciably fractured and mineralized. The origin of the minute mineralized fractures in disseminated copper deposits has long been a challenging problem to the mining geologist, and evidence has been obtained to suggest that the mineralized fractures at Bagdad are related to a regional pattern of conjugate shears which also controlled the location of the dike swarms. The purpose of this paper is to Present this evidence and to emphasize the structural control of the supergene enrichment in forming a chalcocite zone that has provided the ore for the Bagdad mine. The field work on which these conclusions are based was done between October 1943 and August 1945, as a part of the copper investigations of the Goelogical Survey, U. S. Department of the Interior. The writer and his associates, E. A. Scholz and J. D. Strobell, Jr., have prepared a comprehensive report on the geology and ore deposits of the Bagdad area which will be published subsequently by the Geological Survey. Bagdad is located in west-central Arizona in Yavapai County. Ransome&apos; divided the State of Arizona into three provinces: I? the plateau to the northeast; 111, the desert region to the southwest and 11, the moun-

Jan 1, 1949

Coal production during 1963 amounted to 446 mil- lion tons, an anticipated increase of about 6% over the 1962 production of 422 million tons. Electric consumption was 207 million tons, a continuation of its upward trend with an increase of about 7%. The metallurgical market consumed 77 million tons: the industrial market, 96 million tons; and the retail market, 26 million tons. Exports were 46 million tons. Modernization continues in the coal industry as it approaches the mid-1960&apos;s. The industry has shown a keen desire to explore and pursue new developments, new concepts and new managerial methods and techniques that have become so vital and important for industrial well-being.

Jan 2, 1964

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By E. Dow Whitney, Ravrinda M. Chhatre, George Y. Onoda

Phosphate deposits in Florida are a possible source of byproduct uranium. In this paper, the distribution of uranium in several recently mined areas is described. Flowsheets are established for several mines describing how the uranium becomes distributed during the beneficiation of the phosphate matrix.

Jan 1, 1981

By Kefton Teague

The minerals discussed in this section have experienced a gradual, although not spectacular, growth in general. Obvious exceptions are the gradual decreasing use of talc and bentonite as filler materials, partly because of availability and relatively lower sales price of competitive materials. Mineral fillers and filter minerals are used principally in those countries that are heavily industrialized. Except for diatomaceous earth of filter grade, most industrialized countries are reasonably self-sufficient in the various filler and filter minerals. Prices of the various mineral commodities during the period 1950-1970 increased approximately as follows: barite, 43%; diatomaceous earth (filler), 49%; diatomaceous earth (filter), 55%; fuller&apos;s earth, 55%; talc. 77%; and bentonite, 94%. Actual usage of these mineral commodities as fillers and filters, during this period, showed changes approximately as follows: (1) Decrease-fuller&apos;s earth, 6%; talc, 15%; and bentonite, 29%. (2) Increase-barite, 113%; diatomaceous earth (filler), 150%; and diatomaceous earth (filter), -194%. A relationship between the amount of the various fillers and filters used and price increases is apparent. For example, barite increased only 43% in price, but its use as a filler has increased by 113%. On the other hand, talc, which increased 77% in price, decreased in filler use by 15%; and bentonite, which increased 94% in price, has decreased for filler and filter purposes by 29%. The actual decrease in the use of some of these commodities is not entirely caused by an increase in price. Competitive materials frequently have made substantial gains in the various filler and filter markets. For example, much of the bentonite used in the late 1940s and early 1950s for clarification of mineral and vegetable oils has been replaced by competitive materials. BARITE Occurrences and Sources In the United States, barite is produced from about 14 states, listed in approximate order of importance as follows: Missouri, Arkansas, Nevada, Georgia, Alaska, Tennessee, Kentucky, California, New Mexico, North Carolina, Washington, Idaho, South Carolina, Texas, and others. During the 20 years ending in 1970, almost equal amounts of barite were produced from Arkansas and Missouri. Within recent years, Nevada has replaced Georgia as the third leading barite--producing state. West Germany is second to the United States in barite production. Other important barite-producing countries include: Mexico, USSR, Italy, Greece, Canada, and Ireland. Ireland has become an important barite producer only recently. Barite is obtained from vein and cavity fill-

Jan 1, 1976

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.&apos; and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~&apos; have reported the structure of

Jan 1, 1965

By R. H. Richman, II Conard G. P.

AS part of a study of deformation twinning in bcc crystals, solid solutions of beryllium in iron have been found to twin profusely when strained slowly at room temperature. This note reports some crystal-lographic aspects of the operative mechanical twin modes in a quenched Fe-5 wt pct Be alloy. After melting twice under a partial pressure of helium, the alloy was homogenized, cut into pieces 7 to 10 mm on an edge, solution treated at 1130°C,1 and quenched. Debye-Scherrer patterns confirmed

Jan 1, 1963

By Stewart, J. B.

THE property at which this work was done consists of a large deposit of potash salts occurring in massive beds of rock salt, overlain by 600 ft. of salt-impregnated shales and marls. It is in the Province of Cataluiia, Spain, about 45 miles from the railway station of Mauresa and about a mile south of Suria. In addition to sinking the shaft, the program of construction work laid out by the European owners (not Spaniards) included a single-track narrow-gage railroad from Mauresa to the mine; one large office building and several large shop buildings, all of brick and concrete with steel truss roofs; two extensive benches for the future recovery plant; and a large village of stone dwellings for employees. The pay-roll showed approximately 1200 to 1500 men employed. After two years&apos; operation, ending early in the autumn of 1920, the shaft had been sunk 325 ft. and still had an equal distance to go to reach the potash; all tunnels for the railroad were done and the road-bed $0 per cent completed; only a little more than the foundations were completed for all the large buildings, and the excavations of the benches were about 75 per cent done-while only a fair start had been made upon the employees&apos; village. This was the state of affairs when the European owners decided to offer this property under a one-year option to an American syndicate, providing that they agreed to carry on the entire building program and to sink the shaft as fast as was consistent with the quality of work which they demanded, for they wished the shaft to endure at least 200 years.

Jan 1, 1926

By Benjamin C. Craft, Frank Perkins

The wall-building properties of salt-water muds can be maintained at high temperatures by additions of gum karaya, gum ghatti, gelatinized starch, or commercially prepared starch. A germicide should be used to prevent fermentation. Introduction The behavior of drilling mud has received special attention from the petroleum industry within the past few years in numerous research projects dealing with such subjects as chemical treatment, gelation, and filtration characteristics. The importance and control of filtration, or water loss, is readily apparent* It affects the analysis of side-wall cores and interpretation of electric logs; it controls to a large extent the work of primary cementing, reduces the amount of expensive fishing, and permits the running of long strings of casing. It has been found that among the many factors that have an adverse effect on filtration, the presence of electrolytes, in general, and of salt, in particular, is outstanding. The effect is one of flocculation of the colloids due to neutralization of the negative charges on the clay particles. This reaction is further increased on the Gulf Coast because high temperatures reduce dispersion, to a minimum, causing increased flocculation in both fresh-water and saltwater muds. The problem of reducing water loss in salt-water muds by the addition of gums and starch at atmospheric temperature has been investigated,&apos; and many successful field tests in West Texas indicate its solution. From the work of Byck2 it is concluded that no existing method will permit an approximate determination of the filtration rate at high temperatures from data taken at room temperatures. Filtration should be measured at the ternperature actually anticipated in the well, or at least at a number of lower temperatures and extrapolated over a small range. A laboratory study has been made of the chemicals available for the filtration characteristics of salt-water muds at high temperatures, and the use of germicides to prevent fermentation. Laboratory Investigations Procedure Since the purpose of this investigation was to compare several different gums and starches at elevated temperatures, mud from the same source was used for all the tests. Viscosity was measured in a Stormer viscosimeter at 600 r.p.m. and water loss was determined with a Baroid High-pressure and High-temperature Wall-building Tester3 at temperatures from 80&apos; to 250°F. and at a pressure of 500 lb. per sq. in. for 30 minutes. The samples tested consisted of 150 grams of commercial Louisiana mud, 50

Jan 1, 1943

Jan 1, 1944