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By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.' Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By J. H. Canterford

The adsorption of uranium onto Wyoming bentonite was measured in carbonate media over the pH range 8 to 11. Uranium was removed from solution onto the solids by a rapid reaction, proposed to be adsorption of the anionic uranyl tricarbonato complex onto edges of the clay platelets, and a slow reaction that may be precipitation of a hydroxide. The changes in uranium content of the aqueous and solid phases of a uranium ore carbonate leach slurry were also measured as the slurry was progressively diluted. There was an increase in the uranium content of the solids as the pH of the suspension was lowered, as observed with the Wyoming bentonite. Results indicate the conditions that should be met with respect to pH control to prevent the problem of excessive uranium adsorption in the counter-current decantation washing circuit of a conventional leaching process, as well as in the leaching and restoration phases of carbonate solution mining.

Jan 1, 1985

By W. J. Feuerstein

STRUCTURAL imperfections in crystals, in recent years, have received the attention of metallurgists concerned with single-crystal properties. Certain etching solutions cause local variations in the rate of etching at dislocations.' Dislocations are expected to be preferred segregation sites for impurities' and Dash" has shown that precipitation of copper occurs preferentially at edge-type dislocations in silicon. Diffusion rates along dislocations are probably higher than rates through more perfect crystalline regions.' These and other phenomena which may be influenced by dislocations may be studied by revealing dislocations as etch pits. This study was undertaken to develop an etch solution for silicon crystals to reveal low-angle grain boundaries associated with dislocation arrays and also etch pits with good contour definition. Additional etches have been reported by Dash," Vogel and Lovell.T rystals were sectioned on crystal lographic planes at various angles from the growth direction for microscopic examination of the etch pits. Experimental Crystals of 75-100 g mass and 3 cm diam were oriented and cut on crystallographic planes. Crystals were grown by Czochralski technique from a quartz crucible. Lapped wafers were chemically polished in a modified CP-4 etch for 1 min (bromine was deleted from the etch solution). The polished wafer was then etched* at room temperature for 5 min. The use of larger amounts of H2O and/or CH2COOH slows the reaction. The Cu(NO3),.3H2O was added to increase the reaction rate and give more definition to the etch pits developed. Some pertinent features concerning the attack of this etch on silicon can be summarized as follows:

Jan 1, 1959

By F. Valton

In the number of the Engineering and Mining Journal for April 7th, 1877, Mr. W. P. Ward, of Cartersville, Georgia, explains in a very interesting manner, the results he obtained in the manufacture of ferromanganese in the blast furnace. These results may be summed up as follows : Production in the blast furnace of an alloy containing 67.2 per cent. manganese and 3 per cent. of carbon at most, with a utilization of the manganese amounting to 58 per cent. With the exception of the indicated proportion of' carbon, which should be almost doubled to express the true state of facts, we would have had no observations to make on Mr. Ward's paper had he taken into account the results obtained in the same line in other centres of production. Before 1870, spiegel with 8 or 10 per cent. manganese only was known among blast-furnace products. In a journey to Sweden, in 1871,I ascertained that the Schysshyttan works manufactured regolarly a spiegel with 18 per cent. manganese. Later, at the Vienna Exhibition, in 1873, the Sava and Jauerburg works, in Carniola, presented to the jury a ferromanganese, obtained in the blast fur-

Jan 1, 1879

By A. Eilers

In a former paper on Western Smelting Works, I mentioned the great difficulty of obtaining accurate information in regard to the economy of the processes in practice; and to-day, although nearly two years have elapsed since my former paper was written, I am sorry to say that very little improvement has taken place in the keeping of accounts, and in the direction of a more systematic management in the majority of these works. But I am quite certain that by this time even the most sanguine furnace managers must have become convinced, from the experience of the last year, that somewhere in their processes there are enormous losses. Rates for the purchase of ores in 1873 were not as high as they were in former years in certain parts of the country ; labor was no 'higher than formerly; the demand for unparted lead was good throughout the year, with the only exception of the time of the panic, in the fall of 1873; yet there are, of between 40 and 50 works, not more than two or three in Utah and Nevada to-day, that have paid a reasonable interest on the capital invested.

By A. Filers

IN a former paper on Western Smelting Works, I mentioned the great difficulty of obtaining accurate information in regard to the economy of the processes in practice ; and to-day, although nearly two years have elapsed since my former paper was written, I am sorry to say that very little improvement has taken place in the keeping of accounts, and in the direction of a more systematic management in the majority of these works. But I am quite certain that by this time even the most sanguine furnace managers must have become convinced, from the experience of the last year, that somewhere in their processes there are enormous losses. Rates for the purchase of ores in 1873 were not as high as they were in former years in certain parts of the country ; labor was no higher than formerly ; the demand for unparted lead was good throughout the year, with the only exception of the time of the panic, in the fall of 1873; yet there are, of between 40 and 50 works, not more than two or three in Utah and Nevada to-day, that have paid a reasonable interest on the capital invested.

Jan 1, 1875

By Ben E. Lindsly

PetRoleum engineers generally are familiar with the investigations of Dow and Reistle,1 Beecher and Parkhurst,2 and Dow and Calkin3 relative to the solubility of natural gas in crude oil. Since the publication of the results of those investigations and the work of Mills and Heithecker,4 little additional knowledge on this interesting and important subject has appeared in the petroleum engineering literature. The reports of Beecher and Parkhurst and Dow and Calkin agree substantially. The data from both investigations showed that, under the conditions of the tests, the solubility of natural gas in crude oil increased in direct proportion to the pressure at which the gas was put into solution, and the solubility decreased to a considerable extent with increased temperature. These facts, and others relating to the changes in viscosity, surface tension and specific gravity of the crude caused by the solution of gas in the oil, have been given due consideration in the petroleum industry, and the recognition of these facts has resulted in a great improvement in the technique of producing oil. However, in these first experiments, various grades and types of weathered crude oil were contacted at various pressures up to 500 lb. per sq. in. gage with gases deficient to a considerable degree in the heavier hydrocarbons, as compared with the gas that was originally in solution in the oil in its natural underground reservoir. The amount of dissolved gas that was liberated upon reducing the pressure to 1 atm. was measured. For these reasons, the complete significance of the effect of dissolved gases in crude oil, as it occurs in nature, cannot be determined directly from the data obtained under the conditions of the tests as described.

Jan 1, 1931

By C. E. BOCKUSD

WHEN Mr. Bain asked me to lunch with you he requested that I say a few words as to how the Institute could be helpful to the bituminous coal industry. I feel like saying, "Thank you, what have you?" I do not want to trace in detail the story that is old already to many of you. On the other hand it does take some little stage-setting to illustrate what is the matter in the bituminous coal industry, a trouble that must some day be cured. There has been something over a century of bituminous coal production as a real business in this country. True, Joliet and Marquette discovered coal in Illinois in 1673, according to published accounts of their travels, and shortly thereafter Father Hennepin also found Illinois coal in 1689. Coal was mined near Richmond in 1750, and Richmond shipped coal to New York and Philadelphia in 1789. But it was not until 1838 that the production of bituminous coal in this country totaled a yearly output equal to the minimum for one class A mine today, for that was the first year that production exceeded 200,000 tons.

Jan 1, 1930

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By R. W. Vieth, S. A. Bradford

THE orientations of tetragonal tin crystals are commonly examined by either the transmission Laue method or the back-reflection Laue method. The predominant planes and zone axes of the pattern are plotted on a Wulff net and indexed by measuring the angles between planes and directions. The problem of identifying the Laue spots has been approached in several different ways. Nicholas 1 tabulated interplanar angles for ten planes but did not relate the angles to permutation of indices or sign. A table of angles between adjacent planes and of angles between adjacent zones was published by Chandrasekhar and veal.' These tables are very helpful, provided the film shows all the low-order zones that occur within about 20 deg of each other. Frounfelker and Hirthe's compilation3 of angles between the (001) plane and twenty-nine other planes is useful for the indexing, only if the (001) spot can be found on the film. For all but the simplest orientations, however, more information is needed to index the diffraction spots. Standard stereographic projections, such as those published by Bicelli, 4 provide part of the information required. By their nature, these projections show the positions of only a few zone axes. In the tetragonal system many low-order zone axes are not normal to the planes having the same indices. Consequently, planes and directions can have entirely different positions on a stereographic projection. For example, the [011] zone axis is 33 deg from the normal to the (011) plane. The crystallographic orientation usually has to be deduced from a combination of the predominant zone axes and a few low-order planes that appear on the film. In addition to a standard stereographic projection of the planes, a stereographic projection of the directions is needed. Such a projection can be constructed from the angles given in Table I. To provide more information about angles between planes and directions, we have calculated interplanar angles up to (332) and angles between planes and directions up to [332] on an IBM 1620 computer. The angles are differentiated according to permutations of sign and indices. Those doing research on tin single crystals are welcome to request a copy of these tables from the authors.

Jan 1, 1967

By V. A. Phillips, M. Safdar Ali

The tensile properties of Cu-0.20 pct Al, Cu-0.45 pct Mg, Cu-0.27 pct Cr, and Cu-0.22 pct Be solid-solution alloys were studied at -196°, 18°, 2509 and 500°C on wires internally oxidized at 900°and 1000°C. Internal oxidation produced marked increases in yield strength relative to pure copper, particularly at low temperature. The yield strength decreased with increase in temperature to a much greater extent than predicted by current theories of dispersion hardening. The strengthening effect of internal oxidation persisted throughout the entire stress-strain curve, but since a marked loss of ductility occurred at all test temperatures, only modest increases in tensile strength were realized. INTERNAL oxidation involves the preferential oxidation of a baser solute in a relatively noble solvent by diffusion of oxygen into the solid. Since the process is diffusion controlled, it is expedient to carry it out at a high temperature often approaching the melting point. The amount of solute is limited and the oxidation conditions adjusted so that oxygen diffuses inwards to meet the solute causing reaction to progress inwards and form subscale instead of only sur face scale. The reaction can be made to occur throughout the thickness of thin material producing a fine dispersion of oxide inside the metal. C. S. Smith1"3 appears to have been the first to recognize the true nature of the process of internal oxidation. Although extensive kinetic and metal-lographic studies followed by Rhines and coworkers,4-5 Chaston7 andMeijering and Druyvesteyn8 working independently were the first to report hardening effects due to internal oxidation. These results prompted detailed studies of the effects of internal oxidation on the hardness, tensile, creep, and fatigue properties of a number of alloys by G. C. Smith and coworkers9-12 in England, on hardness by Gottardi13 in Italy, and on hardness and tensile properties by wood14 in the U.S.A. Publications dealing with other aspects of internal oxidation will not be reviewed here. Internal oxidation of solutes having a high affinity for oxygen provides a means of obtaining very fine dispersions stable in a suitable atmosphere at temperatures well above those at which most age harden ing precipitates coalesce. The process therefore offers a method of producing thin sheet and wire of possibly outstanding creep resistance. The size limitation might be overcome by internally oxidizing porous powder compacts made from alloy powder before final sintering. PREPARATION OF ALLOYS The alloy ingots, which were approximately 5 1/2 in. long by 1 in. diam, were made up in a high-frequency furnace, using as raw materials OFHC copper, 99.99 + pct Al, high-purity magnesium, and master alloys of Cu-4.19 pct Be and Cu-10 pct Cr. The alloys containing aluminum and magnesium were melted ii closed high-purity graphite crucibles and solidified in the crucible which was lowered partly Out of the coil to give a hot-top effect. The alloys containing beryllium and chromium were made by melting in vacuo in alumina-lined sillimanite crucibles. The magnesium, chromium, and beryllium

Jan 1, 1960

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

The external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied. The theory that has received the most attention recently—that of dislocations—postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped. Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc. Whatever the precise mechanism, the concept of growth is in itself consistent both with the observed low values of critical shear stress and with the experimental observation that slip bands frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleation 2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed 5,6 to precede slip but also predicts certain transient effects in the deformation process. The existence of these transients apparently has not hitherto

Jan 1, 1949

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

THE external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied, The theory that has received the most attention recently-that of dislocations-postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped, Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc, Whatever the precise mechanism, the concept of growth is in itself consistent both with -the observed low values of critical shear stress and with the experimental observation that slip bands. frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleations2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed5,6 to precede slip but also predicts certain transient effects in the deformation process, The existence of these transients apparently has not hitherto

Jan 1, 1948

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By Robert Glass Cleland

THE CLOSING years of the nineteenth century witnessed a rapid expansion in Phelps Dodge activities in Arizona and other parts of the Southwest and a corresponding decline in its exporting and importing interests in New York. Before the close of another decade, this process had gone so far that the company was committed lock, stock, and barrel to its western undertakings. By 1910 the evolution that began with the tentative investments at Bisbee and Morenci was complete. An enormous increase in the domestic production of iron and copper, which made it increasingly difficult to find markets for imported cargoes of those metals from English mills, accounted in part for this radical shift in Phelps Dodge activities and interests. In the case of tin plate, the change was even more spectacular. In 1890 a seventh of the world's supply of pig tin passed through the hands of Phelps Dodge agents. In 1906, thanks chiefly to the McKinley Tariff of 1890 which imposed a duty of over two cents a pound on tin plate imported into the United States, the company received its last shipment of tin from England, and thus ended a form of

Jan 1, 1952

Discussions of the paper of Mr. Gayley read by title at the Lake Superior hieeting, but first presented at the New York meeting of the Iron and Steel Institute, October, 1904 (see p. 746). With the exception of Mr. Pourcel's discussion (p. 1038), these papers are here published under a mutual agreement between the Councils of the two Institutes, and will also be found, with others, in the Journal of the Iron and Steel In-slitute for the pear 1904, Mr. E. Windsor Richards, Past-President,' said that in 1799 Mr. Dawson, of Low Moor, read a paper before a scientific society in York pointing out the great diff'erence in the moisture of the air going into the blast-furnace in the hot months of the year and in the winter months. A cold blast-furnace was a very sensitive instrument, and showed this very clearly, for in June, July and August the furnace did not drive so well; it did not make the quality of iron and required more fuel; so that Mr. Gayley was on the right road to effect an enormous improvement in this direction. He considered that Mr. Gayley was on the way to great success, and hoped that the apparatus would not be a very expensive one. He supposed it mas too early for Mr. Gayley to let them know what the saviug was

Jan 1, 1905

By Carl Wagner

This paper contains solutions of the differential equation of diffusion in binary alloys if the diffusion coefficient is an exponential function of the concentration of one of the components. THE general differential equation for one-dimensional diffusion in a binary system can be written as: where c is the concentration of one of the two components in any suitable units; x, the distance from a reference plane; t, time; and D, the diffusion coefficient. Hartley and Crank&apos; have pointed out that eq 1 with conventional length units for measuring the distance x holds only if the alloy can be regarded as a rigid framework. In general, this is not the case, especially if the lattice parameter varies appreciably with composition. If a modified coordinate system is used instead of an orthodox system based on the centimeter a:: length unit, eq 52 is obtained, which has the same general form as eq 1 and is generally valid. The necessary transformations are presented in the appendix. If&apos; D is independent of concentration, analytical solutions of eq 1 are known for numerous boundary conditions. If D depends on concentration, solutions based on known analytical functions are not available. Among others, Boltzmann2 and Matano3 have shown that the concentration c depends only on (x/t1/2) in the case of diffusion between two semi- infinite spaces with uniform initial concentrations: c = c, for x < 0, t = 0, i.e., x/tl/2 = — x [21] c = c2 for x > 0, t = 0, i.e., x/tl/2 = + a Moreover, Boltzmann and Matano have shown how D may be calculated as a function of concentration over the whole range of composition from c -c, to c = c2 if c as a function of (x/t1/2) for the initial conditions stated in eq 2 has been determined experimentally. Thus, for instance, in principle, the diffusion coefficient in silver-gold alloys may be calculated as a function of concentration for the whole range of composition from only one diffusion experiment with a couple of pure silver and pure gold welded together. If the diffusion coefficient D as a function of concentration c is known, a solution of eq 1 for boundary conditions as stated in eq 2 with arbitrarily chosen values of c, and C2 may be wanted. For instance, if the diffusion coefficient in an alloy A-B as a function of concentration has been derived from an experiment with a diffusion couple involving 0 and 30 pct B as initial. concentrations, the calculation of the concentration distribution in a diffusion couple involving other initial concentrations, e.g., 5 and 20 pct B, may be desired. This problem may be solved by numerical or graphical integration of eq l. The solution of an ordinary differential equation of second order, which results from using (x/t1/2) as an independent variable, can be computed quite rapidly if two conditions for the same value of the independent variable are given. In eq 2, however, two conditions are given for two

Jan 1, 1953

E. Windsor Richards, London, England:—In reading this paper the most interesting point to me mas the question of the maximum percentage of phosphorus allowable in the steel rail. Mr. Colby said, and we will all agree with him, that the engineer knew, and even a steel-rail maker grants that phosphorus is the most undesirable constituent of steel. We in England have been for a long time considering a specification for the supply of steel rails. This matter has been taken up by the Institution of Civil Engineers, the Mechanical Engineers, the Iron and Steel Institute, the Institute of Naval Architects, and the Electrical Engineers. Committees have been formed,and the whole matter has received most careful attention. They arrived at last at an analysis which I will read: " The carbon is to be from 0.35 to 0.5 per cent.; the manganese from 0.7 to 1.0 per cent.; the silicon, not to exceed 0.10 per cent.; phosphorus, 0.07; and sulphur, 0.07 per cent." As to the phosphorus, which is the most important point of all in the analysis, we have for many years, and indeed until very lately, always agreed to supply steel which would not contain above 0.06 per cent. of phosphorus. Iron-ores are not quite as good now as they were formerly, and the manufacturers at the meetings of the committees referred to, tried to obtain an increase in the allowance of phosphorus. They asked the Sub-committee to agree to 0.08 per cent. of phosphorus. They tried all they possibly could to obtain that; but they failed. English engineers in Great George Street and all over England, representing the important Associa tions I have mentioned, would only agree to 0.07 per cent. and that is the maximum allowance of phosphorus. Mr. Colby is an able advocate, but with all his ability he would not have been able to persuade the English engineers to agree to 0.08 per cent.

Jan 1, 1907

By G. W. Thomas

Jan 1, 1967