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By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01' and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-' cm-'). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-' cm-'). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By M. S. Abrahams

Germanium has been rolled in the temperature range of 700o to 800°C. The thickness has been decreased by as much as a factor of four, from a thickness of 0.032 in. to a thickness of 0.008 in. For deformations below 60 pet, the true strain per pass is found to be a constant; from the temperature dependence of this slope, an activation energy of about 2.5 ev is obtained. This energy agrees with that for dislocation climb in germanium . For reductions greater than 60 pet, complete rings are seen in the Lave photographs, new grains are observed in the microstructure, considerable softening occurs, and the hole mobility is very low. This evidence indicates that the recrystallization of gertnanium has occurred. GERMANIUM has been deformed in many ways1 including tension, compression, torsion, and bending since Gallagher2 first described its plastic nature at elevated temperatures. All of these studies indicate that the glide plane in germanium is (111) and that the glide direction is (110). Rolled germanium specimens were used by Kolm, Warekois, and Kulin3 in their X-ray study of deformed semiconductors, but no information is given on the rolling itself. The present experiments deal with the rolling of germanium at various temperatures and for different orientations. In all previous deformation studies, the phenomenon of recrystallization (i.e., the transformation of a single crystal into a polycrystal) in germanium has not been observed4 despite relatively large deformations at elevated temperatures. The proposed reason4 for this was that sufficient energy could not be stored in the deformed germanium lattice. In contrast to the earlier studies this work will present evidence indicating that recrystallization occurs in germanium during rolling at an elevated temperature. I) EXPERIMENTAL PROCEDURE A) Test Specimens. The samples used for rolling were in the form of rectangular parallelepipeds measuring 0.3 in. long, 0.06 in. wide, and 0.035 in. high. They were cut from an undoped single-crystal ingot of p-type germanium with a resistivity of 24.4 ohm-cm, a Hall mobility of 2300 sq cm v-' sec-l, and a hole concentration of 1.1 x 1014 cm"3 at room temperature. The surfaces of the specimens were metallographically polished prior to rolling. The initial dislocation density of the samples was about 10' cm-' as determined by etching in CP4. Two different specimen orientations were used. In the first case, the direction of rolling was parallel to (251), the surfaces in contact with the rolls were of the form (1021, and the normal to the third face was parallel to (211). The corresponding di-

Jan 1, 1964

By V. Runolinna, R. T. Hukki

Preliminary separation of precious metals by flotation can offer a simplification of the conventional method of treatment of anode slimes. Laboratory flotation experiments show that rich gold and silver concentrate can be obtained with excellent recoveries. THE purpose of this paper is to present the results of an investigation into the possibilities of separating precious metals from anode slimes by selective flotation. The work was carried out at the State Research Institute in Helsinki, Finland. The sample of anode slimes tested was submitted by the Outo-kumpu Co. in Finland. In 1947 the average assay of filtered and dried anode slimes in the Outokumpu refinery in Pori was as follows: Au, 0.50 pct; Ag, 9.38 pct; Cu, 11.02 pct; Ni, 45.21 pct; Pb, 2.62 pct; Fe, 0.60 pct; Sn, 1.00 pct; Sb, 0.04 pct; As, 0.70 pct; Se, 4.33 pct; S, 2.32 pct; SO,, 2.17 pct; SiO2, 2.25 pct. The daily assay naturally varies considerably from the figures presented above. The present conventional method of treatment of anode slimes consists of the steps shown in the flowsheet in fig. 1. As seen from this simplified flowsheet, the present method of treatment involves many steps by which the components of the anode slimes are removed one after another until the main products, gold and silver, may be separated. Due to the small scale of operations, the above procedure is carried out in small batches requiring considerable amount of manual labor. If, however, the anode slimes could be treated in

Jan 1, 1951

By V. Runolinna, R. T. Hukki

Preliminary separation of precious metals by flotation can offer a simplification of the conventional method of treatment of anode slimes. Laboratory flotation experiments show that rich gold and silver concentrate can be obtained with excellent recoveries. THE purpose of this paper is to present the results of an investigation into the possibilities of separating precious metals from anode slimes by selective flotation. The work was carried out at the State Research Institute in Helsinki, Finland. The sample of anode slimes tested was submitted by the Outo-kumpu Co. in Finland. In 1947 the average assay of filtered and dried anode slimes in the Outokumpu refinery in Pori was as follows: Au, 0.50 pct; Ag, 9.38 pct; Cu, 11.02 pct; Ni, 45.21 pct; Pb, 2.62 pct; Fe, 0.60 pct; Sn, 1.00 pct; Sb, 0.04 pct; As, 0.70 pct; Se, 4.33 pct; S, 2.32 pct; SO,, 2.17 pct; SiO2, 2.25 pct. The daily assay naturally varies considerably from the figures presented above. The present conventional method of treatment of anode slimes consists of the steps shown in the flowsheet in fig. 1. As seen from this simplified flowsheet, the present method of treatment involves many steps by which the components of the anode slimes are removed one after another until the main products, gold and silver, may be separated. Due to the small scale of operations, the above procedure is carried out in small batches requiring considerable amount of manual labor. If, however, the anode slimes could be treated in

Jan 1, 1951

By A. G. McGregor

IN THE Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 ½ in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining Co.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several . flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally ¼ in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft. from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 ¼ -in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar -water, sodium silicate, and finely ground silica-was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By Juan Sodi, John F. Elliott

The standard free energy of ReS2 has been measured in the range of 1050° to 1250°K using H2/H2S mixtures and a slight variation of the method described by Hager and Elliott.1 The result is: The experimental method and apparatus were modified slightly for this study. Measurements on Cu2S were made to verify the application of the method to the work on ReS2. THE EXPERIMENTS AND RESULTS Briefly, the experimental method consisted of exposing a chip of copper or rhenium at a known temperature for 8 hr to a slowly flowing gas stream at the same temperature in which Ph2S and PH2 were known. The chip was withdrawn quickly from the hot furnace, and subsequently it was inspected for the presence of a sulfided surface. In the experiments described here, there was no ambiguity in any case as to the presence or the absence of the sulfide. At a given temperature, gas compositions for sulfidization were explored systematically until two compositions were found whose values of ?G°, Eqs. [I] and [2], were within approximately 100 cal of each other, one of which was sulfi-dizing and the other was not. These are termed the "straddle" compositions and it is assumed that the equilibrium composition lies between them. The chief modification to the apparatus, which is shown schematically in Fig. 1 of Ref. 1, was to support the metal specimen on a small alumina boat which could be moved along the reaction tube, 6 mm ID, by platinum wires. An appropriate seal at each end of the reaction tube permitted the sample to be moved from the cold end of the tube into the hot zone in 2 to 3 sec, and the sample could be withdrawn equally rapidly. Thus, it was possible essentially to quench the specimen from the reaction temperature with the reaction gas or helium flowing and without danger of breaking the reaction tube. The usual practice at the end of the experiment was to switch the gas system to the helium tank, flood the reaction chamber with helium, and pull the sample out of the hot zone. The purpose of the modification was to permit study of the sulfidization of copper without the complication of the back-reaction between the gas and the specimen as the latter cooled during slow withdrawal of it from the hot zone; this was a problem in the earlier work.&apos; A further improvement located the tip of the temperature-indieating thermocouple and the specimen precisely at the hottest part of the furnace. A carefully calibrated thermocouple, with its tip at the position of the specimen and with other conditions duplicating those of an actual experiment, showed that in the temperature range of 900° to 1122°C the temperature of the specimen differed from that of the tip of the indicating thermocouple by less than 0.5°C. The two positions were 0.5 cm apart. The reaction gas was prepared from ultrahigh-purity hydrogen (<l ppm O2, <0.5 ppm H2O) and CP grade hydrogen sulfide (99.5 pct H2S). High-purity helium (99.995 pct He) was used. All of these gases were purchased from the Matheson Co. All flow meters were recalibrated by the soap-bubble method with hydrogen, H2S, helium, and several gas compositions used during the study. These calibrations gave a linear relationship with a slope of 1.0 for the plot of log flow rate vs log pressure drop across the flow meter, in accordance with the Hagen-Poiseuille equation. The analysis of the gas was determined in the same manner as was reported previously. Good checks were obtained between the composition of the gas established by the flow-meter settings and by chemical analysis of the gas taken after the mixing bulb and ahead of the furnace. The pressures of H2S, H2, S2, and HS in the equilibrium gas at temperature were calculated from the following data :3 The pressures of the species S and S8 were negligible for the conditions of the experiments.3 There was no sign of vaporization of ReS2 either by weight loss or deposits in the reaction tube. Thus it is not possible to account for the apparent volatility of the compound reported by Juza and Biltz.2 The inlet gas composition and the calculated equilibrium ratio of PH2 S/PH2 for the "straddle" points of each experiment are shown in Table I. The specimens of metal for the experiment were small clippings of annealed copper (99.9+ pct) sheet 0.005 in. thick that was obtained from Baker and Adamson and of "high-purity" rhenium (99.9+ pct) sheet 0.005 in. thick that was purchased from Chase Brass and Copper Co. A specimen was removed from the apparatus; inspected for the presence of the sulfide, and then stored in a sealed vial. A fresh clipping was used in each measurement. The condition of the surface of each specimen after the experiment is noted in Table I.

Jan 1, 1969

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

Under the joint auspices of the Illuminating Engineering Society and the University of Pennsylvania there will be given about 20 lectures covering the general principles of illumination and the aspects of lighting practice. They will be held at the University of Pennsylvania in Philadelphia, from Sept. 21 to 28, 1916, inclusive. The subject of illumination of mines will be included in this series, which will be delivered by men selected on account of their qualifications to deal authoritatively with the several phases of the subject. In connection with the lectures there will be an exhibition of the latest developments in illuminating appliances, including lamps, accessories, photometers, together with novel applications of light. There will also be an inspection tour which will include visits to manufacturing establishments, laboratories, lighting companies and notable lighting installations. For further particulars apply to the Illuminating Engineering Society, 29 West 39th Street, New York City.

Jan 6, 1916

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.&apos; The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

Established as a Division February 22, 1928 J J Golden, Chairman M Tenenbaum, Past Chairman Gerhard Derge, Chairman-Elect R W Shearman, Secretary-Treasurer AIME, 29 West 39th Street New York 18, N Y

Jan 1, 1960

Idaho Bureau of Mines and Geology, University of Idaho, Moscow, Ida. John W. Finch, Director. A list of publications will be sent upon application. A series of Bulletins and Pamphlets have been issued by the Bureau to date since 1920 Of the Bulletins, six are out of print, and a charge is made for eight. Each of the Bulletins, in the main, treats of the geology and resources of a particular district in Idaho, as follows (only available Bulletins listed): Bulletin 1, South central Idaho (1920), 15 cents, 7, North central Idaho (1924), 50 cents, 8, Bonneville, Bingham and Caribou counties (1924), 50 cents, 9, Boise Basin (1924), 50 cents; 10, Boundary County (1926), 50 cents; 11, Region about Silver City (1926), 50 cents; 12, Clark Fork district (1930), 50 cents, 14, Eastern Cassia County (1931), 50 cents, Press Bulletin 15, Teton County (1927), Bulletin 16, Melon Valley near Buhl (1927); 17, Concerning land slips near Whitebird, Idaho (1928) The 37 Pamphlets are issued free of cost, and each treats, also, in the main of the geology and resources of a particular district in Idaho Nos 1, 2, 3, 4, 5, 7, 8, 10, 17, 18, 20, 22, 25, 26, 30 and 35 are out of print Of those available, attention may be called to Pamphlet 6, Reported platinum occurrences near Coeur d&apos; Alene (1925), 11, Bruneau River Basin, 12, Power and Oneida

Jan 1, 1933

By H. M. Howe, W. E. C. Eustis

The processes which form the subject of this paper have been experimented on in the laboratory of W. E. C. Eustis, but have not passed beyond the experimental stage. The first is the invention of Mr. J. L. Thomson, of Capelton, Quebec, Canada, the others have been invented by the writers. Thomson&apos;s PRocess foR the Extraction oF Nickel. This consists essentially in first rendering the nickel magnetic, and then separating it from the materials with which it is mechanically vol. X.—20

Jan 1, 1882

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.&apos; Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.&apos; Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy&apos;7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann&apos; and Pilling and Bed-worth. wott and Gurney&apos; have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.&apos; According to Wagner&apos;,&apos;&apos; silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,&apos; silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

By E. C. Bohlen, H. l. Burghoff

THE work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and Glocker;1 Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45° to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (113)[112], (001)[100], and a combination of (110)[115] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,6 who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. TEST MATERIALS AND EQUIPMENT For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, 13 ½ in. wide and 1 ½ in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942