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By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968

By W. A. Backofen, D. H. Avery, G. A. Miller

An evaluation has been made of the relative importance of yield strength (?) and stacking-fault energy (y) to the rate of fatigue-crack growth in materials of fcc structure. Pure copper and its solid-solution al-loys with aluminum and nickel were chosen for the study because they provided sufficient range in both quantities of interest that either could be varied independently of the other. Experiments involved alternating tension and compression of flat specimens which were prepared with sharpened internal notches so that most, if not all, of the crack-nucleation interval could be eliminated. Growth rate (dC/dN) was concluded to be proportional to the square of the plastic-strain amplitude (€,,) over a strain range of approximately 6x 10-4 to 6 x 10-3. The factor, k, linking dC/dN and ep in dC/dN = kEp2 increased and decreased with corresponding variations in y, but it did not respond syste?>/atically to change in ay, indicating that y is the significant variable in crack growth at constant plastic-strain amplitude. In polycrystalline material, k varied by a factor of 5 over the available range of y. In a few single-crystal experiments on Cu-A1 alloys the growth rate responded less strongly to change in y. It has been suggested that single crystals behave somewhat differently than poly crystalline material because there is more extetnsive substructure near the grain boundaries in the latter, and this facilitates crack advance by separation along subgrain boundaries. A point of some controversy in current work on fatigue relates to the effects of strength and stacking-fault energy on crack growth. In recent experiments a separation was made between the cycling intervals for crack nucleation and the subsequent growth that eventually ends a specimen's fatigue life.' The study was carried out on Cu-A1 alloys primarily, fatigued in alternating four-point bending to constant deflection. A nucleation interval of about 10' cycles (at a total strain amplitude = 0.2 pct) was found to be insensitive to aluminum content in the range 0 to 7.5 wt pct, while the growth period was increased approximately forty fold over the same compositional range. The increase was not in any sense linear, however. Rather, most of the change occurred below 4 pct A1 or a stacking-fault energy, ?, of about 15 ergs per sq cm. It was argued that the plastic-strain amplitude was approximately constant, and therefore the effect of composition must have grown out of the reduction in stacking-fault energy. Several studies have shown that, with high ?, cross slip is encouraged, subgrain structure is introduced during fatigue, and cracking is aided through propagation along subgrain boundaries.1-5 Therefore, lowering ? sufficiently to interfere with substructure formation would be expected to retard growth rate. On the other hand, it is a general rule that resistance to fatigue cracking increases as strength is raised. Accordingly, there might still have been some doubt that Y was the controlling variable, since strength would be increased as y was lowered by the aluminum additions. To help in dispelling that doubt, an experiment was made on a polycrystalline Cu-Ni alloy similar in strength to the Cu-A1 alloys but of higher ?; the crack-growth interval was found to be essentially that of pure copper.' Further support for this position on stacking-fault energy as it relates to crack growth is derived from work by Boettner and McEvily,6 in which the actual crack-growth rate was measured on samples previously notched so as to minimize the nucleation period. Unfortunately, it was necessary in isolating strength level to compare different alloy systems and grain sizes. Recognizing the complication, it was still concluded that growth may be retarded by a reduction in y, per se. A related study has also been made by Roberson and Grosskreutz.7 The zinc content of a brass was systematically changed to alter strength and stack-ing-fault energy, although not below the 15 ergs per sq cm at which pronounced change in growth interval was found in the earlier work. The results were limited to more or less conventional S-N diagrams so that nucleation and growth events could not be separated. No definite conclusions were drawn, but

Jan 1, 1967

By L. L. Handy

The development of a theory for miscible liquid displacement requires evaluation of the variables which affect growth of the mixing zone between solvent and displaced oil. Factors which appear to be important are individual fluid viscosities, viscosity ratios, flood rate, fluid densities, flow characteristics of the porous medium and molecular diffusion coefficients of the fluid components. The primary purpose of this paper is to evaluate diffusion effects. Theoretical treatments to date have been limited to floods for which the viscosity ratio is one. Two principal theories have been proposed. Von Rosenberg adapted for porous media a theory derived for capillary tubes by G. Taylor.' ,' In this theory molecular diffusion perpendicular to the direction of flow is a primary factor in sharpening the flood front. Slow floods give sharper fronts for a given distance traveled than fast floods. An alternative theory considers miscible liquid displacement as a statistical problem.3,4,5 Diffusion is not an important factor in this theory, but it leads to the same general type of equation as von Rosenberg's. Both theories predict S-shaped concentration profiles with the same dependence on distance traveled. The statistical or "dispersion" theory predicts rate independence, however. To supplement rate studies a direct measurement of a diffusion effect would be helpful in evaluating which of the two proposed mechanisms best describes miscible liquid displacement for one-to-one viscosity ratio systems. No quantitative theory has been proposed for floods in which a low-viscosity fluid displaces a high-viscosity fluid. It might be anticipated, however, that the extensive fingering observed in floods with adverse viscosity ratios would increase opportunities for an exchange of components between displaced and displacing liquids by a diffusional process. Even if molecular diffusion were not an important mixing mechanism for one-to-one viscosity ratio systems, it could be significant in systems with adverse viscosity ratios. METHOD FOR EVALUATING DIFFUSIONAL MIXING In solvent flooding the displacing liquid can become mixed with the displaced liquid by a number of processes; in general, either mechanical or diffusional in character. To evaluate the contribution of diffusion, a method was sought that would distinguish diffusional mixing from mechanical mixing. Suppose two soluble tracers are added to the displacing liquid and that one tracer has a diffusion coefficient much greater than the other. Then, if diffusion is important during miscible liquid displacement and if diffusional transport is primarily transverse to the direction of flow, substances with high diffusion coefficients will have sharper concentration profiles than those with comparatively low molecular diffusion coefficients. In order to have material balance the profiles for the two tracers must intersect. For one-to-one viscosity ratios the intersection would occur at the 50 per cent concentration point. It is generally assumed that diffusion in the direction of flow is negligible. This assumption appears reasonable because flow velocities are ordinarily orders of magnitude greater than diffusional velocities. If this is not a valid assumption, however, the shapes of the fronts will be further degraded by longitudinal diffusion. The effects of rate and molecular diffusion coefficients are the opposite for longitudinal diffusion to those for lateral diffusion. Higher rates or lower diffusion coefficients would tend to give sharper fronts. The double tracer method offers several unique advantages in evaluating effect of molecular diffusion. First, the method gives a direct measure of the effect of diffusion on mixing zone size. Second, the effect of a difference in diffusion coefficients is determined from a single experiment. Comparison of several experiments at different rates is not required. Third, the method is applicable for any viscosity ratio. Fourth, the method is unaffected by density differences between the two fluids which might result in rate dependent gravity effects. EXPERIMENTAL PROCEDURE Suitable tracers are substances whose diffusion coefficients differ as widely as possible, but whose adsorptions on rock surfaces is negligible. The two tracers selected were methanol and sucrose in water solutions. The approximate diffusion coefficients for methanol and sucrose, as given in the International Critical Tables, are 1.3 X 10-5 and 0.3 X 10-5 m2/sec, respectively. Concentrations in the water solutions were 200 gm/liter of solution for both methanol and sucrose. These high

By H. M. Otte, A. L. Esquivel

A new leasl-squares method is Presented for determining lattice parameters of hexagonal or tetragonul structures. The method is adapted for use on electronic computers and involves a reiterative procedure. The correction factor employed raries linearly with the lattice parameter, a (determined from the Brag, angle). In contrast, Cohen's method and recent modifications of it use a correction factor that varies incersely as the squure of the lattice paramneter, a. While the recent modifications attempt to improve the precision of the extrapolated lattice parameter, a, (or-cu). by stressing the importance of the weighting factor. the present approach emphasizes the need for choosing the correct extrapolation function. A comparison between the present method (the Linear method) and Cohen's method indicates that the Linear method may be more appropriale in certain cases. through a priori no critertion appears to he available for making a chorce between the methods. The size of hexagonal and tetragonal crystal lattices is determined by two parameters, a, and c,. Although in principle the two lattice parameters can be determined independently from reflections for which h - k = 0 and 1 = 0, respectively, in practice this may be inconvenient (because of the angular positions at which these reflections may occur) or not easily possible (because of low intensity). Furthermore, if a high precision or accuracy is required, the limited number of reflections of this type available, particularly in the high-angle region, is not sufficient for the necessary corrections (mainly due to absorption) to be determined with accuracy. Several methods1-7,11-13 have been proposed employing all reflections, to obtain the optimum values, a. and co, either by a trial and error procedure or a least-squares fit. Of the latter method, cohen's5 is the best known one since it provides explicit expressions for the optimum a. and c,. However, Cohen's method is only strictly valid if an extrapolation function is used that varies linearly with l/a2 or lie2 (see Section 3), a requirement that does not appear to be generally appreciated. On the other hand, all the better known and more widely used A recent trial and error method was proposed by Massalski and King8,7 who computed extensive auxiliary tables of axial ratios vs the functions A = [(4/3)(h2 + hk +k2) + l2+(a/c)2] and C = A(c/a)2 used in computing a and c values from the observed Bragg angles. These values of a and c were then plotted against a function which permitted linear extrapolation. As a criteria; for the "optimum" values, Massalski and King rely upon a visual fitting of the line through points representing reflections of low 1-index points to compute the extrapolated value of ao and high 1-index reflections to obtain CO. The successive computations and graphical plotting required to reach the "optimum" value are quite lengthy and tedious even on a desk calculator and no quantitative assurance is obtained of having in fact selected the optimum value.* If the method of Massalski and King is used on an electronic computer, then their published tables become redundant and a least-squares fit becomes a natural selection for the choice of optimum values. Such an approach will be called the Linear method. For work now in progress on the effect of certain physical variables on the lattice parameters of hexagonal crystals, it has become essential to determine the confidence limits of small changes in the lattice parameters. Since extrapolation functions that varied linearly with a and c actually also appeared to vary linearly with l/a2 or l/c2 when tested against published as well as our data, a comparison of Cohen's method and the Linear method was considered desirable (Sections 3 and 4). For the latter method an electronic computer was required since a reiterative procedure to obtain the optimum ao and co values had to be employed. The purpose of this paper is to describe the principles of the Linear method, illustrate its application, and compare it with Cohen's method. 1) THE LINEAR METHOD The standard practice in obtaining the lattice parameters in the Debye-Scherrer method is to

Jan 1, 1965

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By Gen-ichi Nakazawa, Masamichi Fujimori, Ichiro Doi

INTRODUCTION The major products of nickel industry in Japan are the electrolytic nickel (E-Ni), the ferro-nickel (Fe-Ni) and the nickel oxide sinter (NOS), totaling in production to 90 - 100 X 103 tons/year in terms of pure nickel content, and sharing approximately 20% for E-Ni, 10% or less for NOS, and the rest for Fe-Ni. The raw materials to be used for these products depend totally upon the imports from abroad; matte, the raw material used in the production of E-Ni, is from Australia and Indonesia; matte for the NOS is from Indonesia and New Caledonia; and garnierite, the raw material for Fe-Ni, is imported in bulk from New Caledonia, Indonesia and the Philippines. This report describes the acquisition of these raw materials, the production processes, trend of supply-demand, problem areas and the measures taken, and so forth, in connection with the nickel industry in Japan. ELECTROLYTIC NICKEL 1. History The nickel industry in Japan began in 1939 by the Sumitomo Metal Mining Co., Ltd. (SMM) with 150 tons E-Ni/month under the blast furnace smelting and the metal anode electrolysis. This was temporarily suspended after the end of last World War II, but resumed in 1952 with garnierite of New Caledonia as a raw material. Since then, the production capacity has been expanded incidentally to the increase of demand. However, since the smelting of garnierite contained about 2% nickel was very costly, the smelting process had been changed to smelt the briquettes of the mixture of garnierite and nickel sulfide concentrate imported from Canada and Australia. In 1975, this smelter was closed, and SMM's nickel refinery used matte from Western Mining Corp. (WMC) of Australia as a raw material. The refining process had been the metal anode one. The crude nickel oxide derived from roasting the high grade nickel matte had been melted and reduced with coke in the electric furnace and cast into anode. In 1970, a new refinery was constructed to produce 1,000 tons Ni/month under the matte anode process, and further, in 1976, the old refinery was converted into the matte anode process, thus resulting in the total production capacity of 1,690 tons Ni/ month today under the matte anode process. Shimura Kako Co., Ltd. began in 1951 to produce a little of E-Ni, and in 1955, they constructed a shaft furnace smelter with New Caledonian garnierite as a raw material to begin the E-Ni production under the matte anode process. Its monthly production reached 400 tons in 1957, but it discontinued its smeltering in 1963 to convert to the matte import from S. Le Nickel, WMC and INCO. In 1979, it changed the source of matte supply from the above to Soroako of Indonesia, discontinued the E-Ni production in 1979, and arranged for a total toll contract with Sumitomo. Meanwhile, SMM has developed a very distingished process for nickel-cobalt separation and refining by a solvent extraction method from nickel and cobalt mixed sulfide generated as a by-product in the nickel recovering process from laterite under the Nicaro process. Nippon Mining Co., Ltd. (NMC) also developed its own process. The plants under these processes were constructed in 1975, with the monthly production capacity of 230 tons of nickel and 130 tons of cobalt by SMM, and 300 tons of nickel and 110 tons of cobalt by NMC. SMM imports the raw material from the Marinduque Mining and Industrial Corp. of the Philippines, while NMC from Queensland Nickel Pty. Ltd. of Australia. 2. Production Status 2.1 Producers and materials Today, SMM holds the monthly E-Ni production capacity of 1,920 tons, of which 1,690 tons are from the matte anode process, and the remaining 230 tons are from the mixed sulfide as a raw material. NMC also uses the mixed sulfide as a raw material for a production of 300 tons/month. [ ] Most of SMM's raw material, nickel matte, is imported from WMC of Australia, partly using the Soroako matte from Indonesia. An example of material analysis is given in Table 1. Matte is a raw material for E-Ni and NOS, and the major sources of matte supply at present are Australian WMC and Indonesian Soroako, occupying ap-

Jan 1, 1982

and would also contribute to the post-war employment. -As far as the future is concerned, I doubt whether any of the present geophysical methods will ever be developed to directly indicate ore. However, the geochemical methods and certain combinations between chemical and geological methods now used might be the answer to our prayers for direct and more definite methods of determining the quality of the ore or its relative metal content. Geochemical and spectrochemical analysis of minute content in ground waters, in soil or in plants and trees, living or dead, will be extremely important and I would venture to predict that in the very near future each mining or exploration company and each assay oflice will have its own spectroscope equipped for accurate chemical analysis, not only to guide the daily work in the mine, but also for identifying ores as well as for guiding exploration, geological mapping and the evaluation of geophysical indications. These methods, although they are still in their infancy, promise very much for the future. Radioactivity methods could also be helpful when sufficient facilities for radioactivity determination can be made available. They have already been used to a great extent in oil exploration and experiments have shomn great promise for ore exploration also. As for future surveys of large areas, the exploration for physical contrasts will be made from the air, using aeroplanes, helicopters, etc. Already electrical and magnetic methods have been designed whereby the instruments are carried in the aircraft and by automatic recording the location of anomalies is made in a simple enough manner. It should be possible in this way to cover, say, a square mile in an hour. Later Discussion Replies to Dr Lundberg. J. B. Macelwane.*—Someone has said that if a person knows his subject well enough he can explain it in words of one syllable. The point is well taken and I think the converse is also true. If a person cannot explain a subject clearly in simple words, it is either because he has not sufficient command of the language, or he is not master of his subject. Now it is obvious, it seems to me, that the remedy for both of these unfortunate conditions lies not in less education, but in more. If Dr. Lundberg has met geophysicists who confused and discouraged prospective clients by their inability to talk the language of the mine owner or of the mining engineer or geologist, the fault most probably lay in the geophysicist's lack of sufficient training; but it may also have been the want of ordinary common sense, which no amount of education can supply. It is hard to understand the position taken by Dr. Lundberg. Does he regret his own extensive training? noes he wish to say that he would have had greater success in geophysics if he had been only a mine hand with an instrument and a rule of thumb? As a matter of fact, I find it rather difficult to account for his presentation before this Committee on Geophysics of an emotionally distorted picture of the Report of the Committee on Geophysical Education, after the lapse of an entire year since the Report was read and discussed in its proper place, unless he honestly thinks he is handicapped by his knowledge and training and wishes to warn the whole profession against a similar fate. I regret that I am obliged to disagree so emphatically with Dr. Lundberg's thesis— but I believe it would be dangerous if left unchallenged, both because of the inaccurate statements it contains concerning the recommendations made in the Report and because of the ultimate discredit that would be bound to fall upon genuine geophysics if Dr. Lundberg's recommendations were extensively followed out. S. F. Kelly.*-—The argument that a science and its practitioners can be improved by debasing the standard of educational preparation is indeed a strange argument to come from the pen of a man with the education of Dr. Hans Lundberg. In criticising the Committee report, moreover, he has to a certain extent set up a straw man to belabor. The statement that the Committee report recommends that

Jan 1, 1946

and would also contribute to the post-war employment. -As far as the future is concerned, I doubt whether any of the present geophysical methods will ever be developed to directly indicate ore. However, the geochemical methods and certain combinations between chemical and geological methods now used might be the answer to our prayers for direct and more definite methods of determining the quality of the ore or its relative metal content. Geochemical and spectrochemical analysis of minute content in ground waters, in soil or in plants and trees, living or dead, will be extremely important and I would venture to predict that in the very near future each mining or exploration company and each assay oflice will have its own spectroscope equipped for accurate chemical analysis, not only to guide the daily work in the mine, but also for identifying ores as well as for guiding exploration, geological mapping and the evaluation of geophysical indications. These methods, although they are still in their infancy, promise very much for the future. Radioactivity methods could also be helpful when sufficient facilities for radioactivity determination can be made available. They have already been used to a great extent in oil exploration and experiments have shomn great promise for ore exploration also. As for future surveys of large areas, the exploration for physical contrasts will be made from the air, using aeroplanes, helicopters, etc. Already electrical and magnetic methods have been designed whereby the instruments are carried in the aircraft and by automatic recording the location of anomalies is made in a simple enough manner. It should be possible in this way to cover, say, a square mile in an hour. Later Discussion Replies to Dr Lundberg. J. B. Macelwane.*—Someone has said that if a person knows his subject well enough he can explain it in words of one syllable. The point is well taken and I think the converse is also true. If a person cannot explain a subject clearly in simple words, it is either because he has not sufficient command of the language, or he is not master of his subject. Now it is obvious, it seems to me, that the remedy for both of these unfortunate conditions lies not in less education, but in more. If Dr. Lundberg has met geophysicists who confused and discouraged prospective clients by their inability to talk the language of the mine owner or of the mining engineer or geologist, the fault most probably lay in the geophysicist's lack of sufficient training; but it may also have been the want of ordinary common sense, which no amount of education can supply. It is hard to understand the position taken by Dr. Lundberg. Does he regret his own extensive training? noes he wish to say that he would have had greater success in geophysics if he had been only a mine hand with an instrument and a rule of thumb? As a matter of fact, I find it rather difficult to account for his presentation before this Committee on Geophysics of an emotionally distorted picture of the Report of the Committee on Geophysical Education, after the lapse of an entire year since the Report was read and discussed in its proper place, unless he honestly thinks he is handicapped by his knowledge and training and wishes to warn the whole profession against a similar fate. I regret that I am obliged to disagree so emphatically with Dr. Lundberg's thesis— but I believe it would be dangerous if left unchallenged, both because of the inaccurate statements it contains concerning the recommendations made in the Report and because of the ultimate discredit that would be bound to fall upon genuine geophysics if Dr. Lundberg's recommendations were extensively followed out. S. F. Kelly.*-—The argument that a science and its practitioners can be improved by debasing the standard of educational preparation is indeed a strange argument to come from the pen of a man with the education of Dr. Hans Lundberg. In criticising the Committee report, moreover, he has to a certain extent set up a straw man to belabor. The statement that the Committee report recommends that

Jan 1, 1946

By E. T. Turkdogan, L. E. Leake

A number of measurements have been made on the vapor pressure of pure iron at 1600°C. Experiments were carried out by the transportation method in which a sample of iron is exposed in a furnace to a stream of pure argon, metered at a predetermined flow rate for a specified period of time. The vapor pressure was obtained from the weight loss of the sample. A detailed diagram of the apparatus used for the experiments is given in Fig. 1. It consisted of a horizontal molybdenum-wire-wound furnace fitted with a recrystallized alumina tube 1 1/8 in. internal diam. The boats, 1 by 3/16 by 1/8 in., were fired in argon at 1600°C to constant weight before use. After this treatment, subsequent heating of the boats to 1600°C gave little or no further change in weight, e.g. ±0.05 mg in 24 hr. The furnace and reaction tube were separately fed with argon from two independent flowmeters. These were connected to a common supply source via an argon purification furnace containing metallic titanium sponge at 700°C, and an anhydrone drying-tower. A rotary displacement-type meter was included in the gas train to provide a direct means of measuring the total volume of gas passed through the reaction tube. The material used was vacuum melted high-purity iron in the form of wire 2mm in diam. The following impurities were present in the iron: 0.008 pct C, 0.002 pct Si, 0.005 pct Mn, 0.008 pct S, 0.001 pct P, 0.01 pct Ni, 0.001 pct Cr, 0.006 pct Cu, and 0.001 pct Al. Samples consisting of three small pieces of this wire were laid end to end in a recrystallized alumina-combustion boat, and were separated by small fragments of alumina. The wire samples were then melted in argon to form spherical beads 2 to 3 mm in diam. After weighing, the boat with its contents was placed on the boat carrier and introduced into the cool end of the reaction tube. The entire furnace system was then flushed with argon for 30 min. At the end of this period, the flow of argon to both furnace and reaction tubes was adjusted to the desired level; then the boat was slid rapidly into the hot-zone of the reaction tube. After a known volume of gas had passed through the reaction tube, the boat was withdrawn quickly to the cool end of the furnace. When quite cool, the boat was removed from the fur-mace and placed in a desiccator for subsequent re-weighing. The semi-micro balance used in these experiments had a sensitivity of 0.005 mg. The above procedure was repeated at several flow rates within the range of 25 to 300 ml per min. The flow of argon in the annular space between the two tubes was at a rate of 300 ml per min in all experiments. During all the experiments the furnace temperature was maintained at 1600° ± 5°C by means of a temperature controller. The temperature of the reaction zone was measured with a Tinsley high precision disappearing filament pyrometer which was initially calibrated against a Pt-13 pct Rh/Pt thermocouple; the errors due to temperature measurements were within * 5°C. RESULTS Assuming that the iron vapor is in the monatomic state, the vapor pressure can be calculated from the weight loss of the sample and the volume of the carrier gas. The results obtained are plotted in Fig. 2 against the rate of flow of argon through the chamber containing liquid iron beads. At low flow rates, the thermal diffusion of iron gives an apparent high vapor pressure, but at high gas flow rates, the carrier gas is not saturated with the vapor, and therefore, low vapor-pressure values are obtained. This is now a well-known phenomenon. There is a distinct inflexion of the curve at about 120 to 160 ml per min rate of argon flow and the vapor pressure of iron within this

Jan 1, 1961

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By H. Sigurdson, T. V. Cherian, C. H. Moore

The phenomenon of recovery of cold-worked metals is interesting not only because of its practical importance but also because of its fundamental significance in solid state reactions. Although extensive investigations1,2 have already been made in an attempt to discover the mechanics of the recovery process, many of the observations have not yet been satisfactorily correlated to provide a completely consistent model for the process. The wide differences in the recovery rates of various properties can be cited as a typical example of one of the difficulties that are encountered. Frequently, for example, the electrical resistance will have almost completely recovered before any recovery in tensile strength can be detected. Of course, such differences in the recovery rates of different properties might be explained by assuming that each property is a unique function of the work-hardened state, and consequently each property exhibits its own unique recovery rate. The assumption that different properties are uniquely related to the work-hardened state cannot be denied. On the other hand, the properties that recover at different rates often exhibit more or less parallel changes upon work-hardening. This suggests that the microstructural changes attending recovery are not exactly the reverse of the changes attending work-hardening. Several types of imperfections must be postulated in order to account for this apparent anomaly. The different recovery rates for various properties, then, are due to the different recovery rales of the type of imperfection to which each property is most sensitive as well as the unique dependence of each property on the cold- worked state. This concept assumes that a simple model of the work-hardened state consisting only of one type of imperfection, such as Taylor's type of dislocation patterns, is inadequate to cope with the diversified phenomena attending work-hardening and recovery. Although current models for the work-hardened state are not useful for describing all aspects of the recovery process, the general trends of the recovery of each postulated type of imperfection as a function of time and temperature should be at least qualitatively deducible from the rather well developed laws of kinetics of reactions in the solid state. Consequently, recovery data might prove useful for elucidating some aspects of the complexities of the work-hardened state of metals. A preliminary attempt to study work-hardening by investigating recovery rates of cold-worked metals is outlined in the following pages of this report. Experimental Procedure Many properties recover when cold-worked metals are annealed below their recrystallization temperature. Therefore, electrical resistivity, thermal electromotive force, X ray diffraction line widths, X ray diffraction line intensities, elastic spring back, density and other physical and chemical properties have been used to study the recovery process. Major interest, however, has generally been directed toward the recovery of the mechanical properties such as hardness, yield strength, and tensile strength. But a search of the literature suggests that the effect of recovery on the true stress-true strain curve has been neglected, in spite of the current recognition of the fundamental importance of such an investigation. An investigation on the effect of recovery treatment on the true stress-true strain curves in tension, therefore, was undertaken in the present study. Commercially pure aluminum (99. + pet Al) in the form of 0.100 in. thick rolled sheet of 2S-O aluminum alloy was selected as the material for this investigation because rather extensive correlatable data are already available on the recovery of some of its properties. Tensile specimens having a 6 in. long gauge section and a uniform reduced section width of 0.500 in. were machined from the sheet in accordance with a design that has previously been reported.3 All specimens were selected with their axes aligned in the rolling direction. In order to eliminate the effects of previous work-hardening and the effects of machining, the specimens were annealed for 15 min. at 750°F before testing. During tensile testing the loads were measured by means of a proving ring (sensitive to 1/2 lb) in series with the specimen.4 Strains were determined from the extension of a rack and pinion strain gauge sensitive to a strain of + 0.0001. The stress was recorded as the true stress, namely

Jan 1, 1950

By H. I. Aaronson, C. Wells

Configurations of ferrite crystals have been found in a plain carbon steel which appear to have resulted from the nucleation of new ferrite crystals at the interphase boundaries of previously formed crystals despite the high carbon concentrations which necessarily develop at these boundaries. This phenomenon has been termed sympathetic nucleation. An attempt has been made to reconcile the occurrence of sympathetic nu-cleation with current nucleation theory. THIS investigation is one of a series on the formation of proeutectoid ferrite from austenite. From the viewpoint of chemical composition, this reaction consists of the nucleation and diffusional growth of crystals of carbon-poor ferrite within a matrix of carbon-rich austenite. The austenite adjacent to the austenite-ferrite boundaries will be greatly enriched in carbon, approximately to the value of the y/(a + y) equilibrium curve or its metastable extrapolation at the temperature of transformation. Those areas of austenite appreciably farther removed from the growing ferrite, on the other hand, will be relatively unaltered in composition, especially at the earlier stages of transformation. Since rates of nucleation are considered to decrease exponentially with decreasing supersaturation,' the frequency with which ferrite nuclei appear at austenite-ferrite boundaries should be negligible in relation to that at which they form in other regions of the austenite. During this investigation, however, many groupings of ferrite crystals have been found which appear to have resulted from the nucleation of ferrite at austenite-ferrite boundaries. This phenomenon has been given the name of sympathetic 71.1tcleation. A number of micrographs of morphological configurations caused by sympathetic nucleation will be presented, after which an explanation for this reaction will be proposed in terms of current nucleation theory. Some of the structures to be considered are composed of bainite, an aggregate of ferrite and carbide, rather than of ferrite. Since ferrite and bainite differ only in that bainite forms under conditions which result in the nucleation of carbides behind the advancing austenite-ferrite boundaries,' it will usually be unnecessary, for the purpose of this paper, to distinguish between the two reaction products. All studies were performed on an electric furnace steel (obtained from the Vanadium Alloy Steel Co.) containing 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was cast as a 150 Ib, 7x7 in. cross section ingot and forged into bars 2x2 in. in cross section. These bars were homogenized for 48 hr at 1250°C in an Endo-Gas atmosphere. The depth to which decarburization penetrated during this heat treatment was determined by chemical and microscopic analyses and the affected metal was removed by machining. Specimens for isothermal transformation studies were cut from the remaining material; most of these specimens were 1/2x1/4X1/16 in., though some with a thickness of 1/32 in. were prepared for use at the shorter reaction times and lower reaction temperatures. Specimens were austenitized for 30 min at 1300°C, isothermally reacted for various times at temperatures ranging from 775" to 475 "C, and then quenched in iced water. The austenite grain sizes within individual specimens ranged from ASTM Nos. 1 through —4. A commercial heat-treating salt which was continuously deoxidized by an immersed graphite crucible served to minimize the loss of carbon during austenitizing; thick covers of powdered graphite and immersed graphite rods effectively prevented decarburization in the lead pots employed for the isothermal reaction treatments. The heat-treated specimens were sectioned and mounted in Bakelite. Following the completion of standard grinding and mechanical polishing procedures, the specimens were electrolytically polished with a Buehler-Waisman apparatus and etched in 2 pct nital. Experimental Results Rules of Evidence for Sympathetic Nucleation—On the basis of observations made on a single plane of polish, one precipitate crystal may be considered to have been sympathetically nucleated at the inter-phase boundary of another precipitate crystal when the following conditions are fulfilled: 1) The sympathetically nucleated crystal is not in contact with a grain boundary or a subboundary in the matrix phase. 2) The shape, size, and location of the crystal at whose boundary sympathetic nucleation occurred (hereafter termed the base crystal) and the crystal formed by sympathetic nucleation substantially pre-clude the possibility that the plane of polish em-ployed may have concealed the fact that both crys-tals actually nucleated at a grain boundary or a sub-boundary in the matrix phase.

Jan 1, 1957

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A' and Stage B'. Stage A' type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B' type from -80 x 10-6 to -800 x 10'6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A' and Stage B' deformation are briefly reviewed. 1) Stage A'. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10' cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B' there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965