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By G. C. Gester

With the exception of exploration geological work that is being prosecuted in various parts of the mainland of Arabia, the only new developments in Arabia during 1934 were on Bahrein Island, which is in the southwestern portion of the Persian Gulf, approximately 25 miles from the mainland of Arabia. Here the Standard Oil Co. of California, through its wholly owned subsidiary, The Bahrein Petroleum Co., Limited, has continued to carry on a systematic drilling campaign and has constructed camps, pipe line and marine loading facilities. During 1934 eight wells have been completed at depths ranging from 2058 to 2253 ft. These wells have shown average initial productions ranging from 1500 to 5000 bbl., with one, No. 15, estimated as being capable of flowing as much as 11,000 bbl. per day. The oil is asphaltic in character and has a gravity range of from 32' to 34' A.P.I. The locating of all new wells has followed a plan of orderly development, with the ultimate object of obtaining efficiency of operation and maximum production. The wells are taking a penetration of 200 to 250 ft. of the lower or so-called Main productive zone. The upper oil zone, which is cased off, includes 300 to 400 ft. of alternating limestones, clays and shales and carries a heavier oil under lower pressures. The Main zone is similar lithologically to the upper zone. Micro-fauna collected from cores have shown that the oil occurs in formations of lower Eocene and Cretaceous age. Development to date has not progressed sufficiently so that either the maximum thickness of the oil-bearing horizons or the limits of the field can be determined. Something over 10,000 acres has been proven to date. Among other developments leading toward the marketing of oil from Bahrein during 1934 was the construction of a marine loading terminal. This included the laying of over 3 miles of 12-in. submarine pipe line from the small island of Sitra out into the harbor, terminating in 50 ft. of water; also the laying of more than 10 miles of gathering lines from the producing area to the terminal. Three crude oil working tanks with floating roofs were erected on Sitra Island, having a capacity of 250,000 bbl. A pumping plant was provided having a capacity of 5700 bbl. of oil per hour. This is housed in a dustproof building, as rather severe

Jan 1, 1935

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By Y. C. Liu

THE existence of mechanical twins in bcc metals has long been known. With recent intensive interest in the mechanism of twin formation and its role in plasticity and crack initiation, a study of the general Characteristics of twin intersection appears pertinent. The scope of the present note will be limited to the crystallography of the twin intersections of (112) twins, without consideration of its mechanism, movement of atoms, crystal structure, or the strain energy involved at such an intersection. The twinning elements of (112) twins are considered to be K1 = {112}, n1 = (111) and K2 = {112}, n2 = (111) with a twin shear of 0.707. The crystallographic features of twin intersections have been worked out in detail by Cahn.1 The present work applies the general principles postulated by Cahn to the intersections of (112) twins. The basic conditions for the twin intersection are: 1) The trace of crossing (A) and the secondary (C) twins in the planes of the crossed twin (B) must be parallel. 2) The direction (n1) and magnitude (s) of shear must be identical in the crossing and secondary twins. Also the sense of shear must be the same. These two conditions have to be fulfilled in order to maintain geometrical continuity at the twin interfaces. Fig. 1 shows the perspective representation of how these two conditions are fulfilled at the intersection. This type of intersection will be named Type-I. It is the purpose of this note to point out the existence of another type of intersection, Type-II, as shown in Fig. 2. In this type of intersection, the crossing twin A remains straight and the crossed twin B has been bent. The two conditions laid down by Cahn must also be met. This leads to the following corollary conditions: 1) The interface between twins B and C must be parallel to the twin habit of crossing twin A. 2) n1c must be parallel to n1A. 3) The twin shear (s) of twin C must be exactly equal to and in the same sense as that of crossing twin A. Thus, in order for the Type-II intersection to take place, the twining elements of secondary twin C must fulfill the above three conditions with respect to crossing twin A. Let K1 of crossed twin B be (112). All indices of the matrix can therefore be converted into new in-

Jan 1, 1963

By William Kent

ABOUT a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh. Car-wheel Works, in making a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and pro¬vided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to , 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0088 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam was told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hand-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 44,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By William Kent

About a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh Car-wheel Works, in malting a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and provided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0085 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam wits told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hantl-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 34,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of' the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece. must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

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 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 S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 ' RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.' By

Jan 1, 1970

By R. G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and

Jan 1, 1952

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less.

Jan 1, 1938

By David W. Brunton

(San Francisco Meeting, October, 1911.) MINE-DRAINAGE and the ever-increasing demand for water on the plains have within the past few years necessitated the driving of a great number of adits and tunnels, including many of considerable size and great length. In most instances, ex isting conditions have called for extreme rapidity of execution; and this necessity, coupled with the high altitudes at which most of the work has been carried on, excessive freight-rates, and difficulty -of access, has involved many complex and interesting problems. One of the most rapidly executed undertakings of this class is the Laramie tunnel, recently completed for the Laramie-Poudre Reservoirs & Irrigation Co. This tunnel is driven through Green ridge, a spur of the Continental Divide, which separates the Laramie river from the Cache-la-Poudre in Laramie county, Colo. Green ridge is extremely persistent, and further northward in Wyoming is known as Sherman hill, the highest point on the Union Pacific railway. At the point where the tunnel is driven, two opposing bends bring these streams within 2.5 miles of each other, with a difference in elevation of 500 ft. The rock exposed on the banks of the two rivers does not differ materially in hardness; and, without a geological study of the conditions involved, it would appear that the difference in the depth of erosion of the two streams is due principally to the greater volume of water at this point in the Cache-la-Poudre, which has a drainage-area above the tunnel-portal of 110 sq. miles, as against 30 sq. miles of natural drainage for the Laramie. To increase the water-supply at the tunnel, however, this latter amount has been augmented by two side collection-canals, which bring the available drainage-area up to 84 square miles. The nearest railroad shipping-point to the eastern portal is

Apr 1, 1912

By C. Schlumberger

SINCE the beginning of .the year 1928 the senior authors and their associates have applied a series of procedures which makes possible the detailed study in situ of the formations traversed by a drill hole before the casing has been landed. They have given the name "electrical coring" to the ensemble of these processes, which now replace in a large measure the mechanical coring performed by the drillers, and permit the gathering of bottom-hole data hitherto unobtainable. Three years have elapsed since the technique and interpretation of these measurements emerged from the experimental stage and entered the field of industrial application on a large scale. The total length of drill holes so far surveyed by the authors and their associates, all over the world, amounts to several millions of feet. Practical and strongly built equipment has been evolved, which permits the examination in a short time of an open hole several thousand feet long. No comprehensive paper has yet been published discussing the essential principles of the processes applied and bringing into evidence their economic interest. This is the object of the present paper.1 Numerous examples of field work performed under varied geological conditions are given, constituting a concrete illustration of the services rendered by the new methods. The study in situ of the formations penetrated by a drill hole is based on the measurement of a given physical factor or parameter associated with these formations. Generally. the measurements are made syste-matically along the whole length of the open hole. The physical factors or parameters which are now utilized by us to this end are: (1) the resistivities of the rocks; (2) their porosity; (3) their electrical anisotropy; (4) their temperature; (5) the resistivity of the muds. In order to

Jan 1, 1932

By R. W. Winson

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series+rocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18014 to 300A units, while the amphibole fibers are many times larger in cross section. Electron micrographs of the more common types of as- bestos are shown in [Figs. 1-4]. [Fig. 1] illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in [Figs. 5-7] clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si,O,l and brucite [Mg(OH),] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures.

Jan 1, 1975

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C.A. Zapfee, C. E. Sims

An investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. Apparatus The apparatus is shown in Fig. r and the system is shown by diagram in Fig. 2. Furnace, A lmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In this furnace fres oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1943

By C. A. Zapfee, C. E. Sims

An investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. Apparatus The apparatus is shown in Fig. r and the system is shown by diagram in Fig. 2. Furnace, A lmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In this furnace fres oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1943

By Paul Merica

ALTHOUGH nickel was discovered and isolated as early as 1750 and its valuable properties recognized, many years passed before it was used commercially for wire, sheet, rods, etc., in the pure form. This was due partly to its high cost at that time and partly to the fact that it was not possible to refine and cast nickel into ingots sufficiently malleable to be amenable to the usual forging, rolling, or drawing processes. So remarkable was this fact, and so different from the experience at that time with metals such as copper and iron, that it has left its impress on the no-menclature within the nickel industry. To this day, furnace-cast nickel produced in such a manner as to be suitable for rolling and forging is called malleable nickel to distinguish it from the ordinary pig and shot nickel of commerce. In 1878, the firm of Jos. Wharton, of Philadelphia (which later became The American Nickel Works, a constituent of The International Nickel Co.) exhibited at the Paris Exhibition specimens of rolled pure nickel strip and of drawn nickel wire. About this time, there was considerable activity in the study of the refining of nickel and several methods were described, some of which were patented, for the production of furnace-cast malleable nickel including the use of manganese (Boed-dicker,1 Selve and Lotter2), the use of potassium permanganate (Bernsdorfer Metallwarenfabrik3) and the use of phosphorus (Garnier4). By far the most efficient method was discovered by Th. Fleitmann in 1879;5 it consisted in adding to the molten nickel, just before pouring the castings, from 0.05 to 0.125 per cent. of metallic magnesium. This soon became the recognized final malleableizing treatment for furnace-cast nickel.

Jan 1, 1925

By H. S. Geismer

INTRODUCTION. THERE are three general methods available for obtaining commercial brown iron-ore : hand-screening; washing; and washing and concentrating. Hand-screening has produced a large tonnage of ore in the past, but is rapidly falling into disuse, except as a preliminary step, largely because modern furnace-practice requires all foreign material to be separated from ores before they are delivered to the furnace, and hand-screened ores can rarely be made to fulfill that requirement. Another argument against hand-screening is, that the waste-pile often contains as much ore as the screen recovers. The operation known as hand-screening consists of throwing the ore-bearing material against a stationary inclined screen of 0.5- to 0.75-in. mesh, similar in construction to the screens employed in sand-pits. The recently-prospected brown-ore deposits of Cuba seem to offer possibilities for hand-screening not possessed by the average American deposit, since these ores are not associated with worthless clays. Washing, and washing and concentrating, may be discussed together, since concentrating is never practical on brown iron-ore, except to treat ores that have already been washed. (Strictly speaking, washing might be classed as concentrating, but it is never so designated by brown-ore men.) The various steps of removing ore-bearing material and converting it into ore suitable for blast-furnace use, may be grouped under five heads: loading for transportation ; transporting ; feeding into the washer; washing; and concentrating. These five subjects will be considered in consecutive order. Each of these successive steps may be accomplished in a number of different ways, the choice depending entirely upon the character of the ore-bearing material to be treated.

Aug 1, 1911