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By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested' and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio's waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded 'by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.' However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan'tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m'ay offer greater restriction to the production of

Jan 1, 1967

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d'Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.' The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.' The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.' The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By Willis T. Burns

I. Introduction.......................................... 703 II. History................................................ 703 III. General Description of Plant......................... 704 IV. AnoDes................................................. 711 V. Cathodes............................................... 714 VI. Electrolyte............................................ 718 VII. Electrolytic Slime..................................... 727 VIII. Power................................................. 728 IX. Operating Details..................................... 732 X. Furnace Refining...................................... 736 XI. Physical Testing oF Products.......................... 739 I. Introduction. These notes are submitted, not as a discussion of the modern practice of electrolytic-copper refining, but as the record of a refinery that was among the pioneers in the field and that is to-day, and has been for 17 years, operating under conditions not to be found in any similar plant in the country. I refer to the current density, which is at least 60 per cent. higher than that regularly employed elsewhere, and to the fact that the anodes treated are the direct product of the converter rather than of the reverberatory furnace. The writer has no knowledge of any other refinery treating anodes of this character. II. History. This refinery, now one of the oldest plants of its kind operating in this country, was built in 1892 by the Boston & Montana Consolidated Copper & Silver Mining CO. to refine the product of its Great Falls reduction works. The estimated capacity of the plant as designed was 65,000 lb. of cathodes per day at a current density of 16 amperes per square foot.

Jan 1, 1914

By H. l. Burghoff, A. I. Blank

The state of knowledge bearing on the stability of copper under stress at elevated temperatures is generally known to be in need of revision and extension. The present investigation, dealing with the creep characteristics of a deoxidized copper of low residual phosphorus content, is intended to contribute in some small measure toward this end. The experimental data presented herein have been correlated by methods of evaluation and interpretation familiar to those who are concerned with crecp of metals. In practice it is common, if not requisite, to use structurally stable materials at elevated temperatures. It is frequently desirable, however, to test materials under conditions that produce structural change, in order to determine the extent of such change and its effect on physical properties, thus making it possible to establish accurately the limiting conditions to which such materials may be safely exposed. The creep characteristics of the drawn copper wire of this investigation arc directly associated with its structural instability at elevated temperatures. Complete realization of this fact is essential to the evaluation of its creep resistance under various conditions. Creep results should apply to steady deformation under equilibrium conditions, but these are seldom attained in only one or two thousand hours. It will be shown that steady creep rate for copper at useful stresses does not usually begin until considerably more time has elapsed. A wholly satisfactory substitute or shortcut for extensive creep testing does not appear to be evident in the application of mathematical analyses to limited experimental data. Material A single lot of phosphorized copper wire was drawn down to 0.125-i11. diameter with a final reduction of 84 per cent. After mechanical straightening, a portion of this wire was annealed to an average grain size of 0.013 mm. in a controlled-atmosphere furnace. The composition and initial properties of the copper in these two conditions are listed in Table I. Photomicrographs of the original structure are shown in Fig. I.

Jan 1, 1945

By Percy A. Robbins

The central power-station of the De Beers Consolidated Mines, Ltd., was designed and built under my supervision about five years ago. Since no detailed description of this plant has ever appeared, it may possess sufficient interest to arrant its publication, even at this late date. Although some additions may have been made to the plant, the following account, prepared from my notes, and accurate up to May, 1905 (at which time I severed my connection with the De Beers Company), will, I think, be found substantially correct. Certain local conditions governing the design of this plant should be stated first. IT. General Considerations. The climate is hot and dry. The region around Kimberley is arid and water is very scarce. The supply obtained from the mines contains so much material in solution that it is unfit for use in boilers or condensers (although tests recently made with a water-softening plant, built by Hans Reisert, of Germany, would indicate that water thus treated is suitable for boilers). And the amount of water required for concentrating about 30,000 tons of ore per day is so large that the question of adequate water-supply for this power-station had to be carefully considered. The rainy season extends from December to April, and the rainfall averages about 15 in. per year. Droughts are frequent; and in some years there is scarcely any rain at all.

Jan 1, 1909

By F. K. Spragins

Growing demand for conventional crude oil in North America in the face of diminishing sup- ply is bringing about increased interest in synthetic fuels. With one commercial plant already in full production, another in the planning and engineering stage and still others being seriously considered, the Athabasca tar sands are proving to be a leading center of interest. Here, and in the closely related deposits, reserves in place total over 700 billion barrels.' When and if fully developed, Athabasca tar sands could make both Canada and the United States substantially independent of all off-shore supplies of crude for many years to come. Its product, a high-quality, low-sulfur synthetic crude, is beginning to enter the market place at a most favorable time. Oil Deposit The main body of Athabasca tar sands, about 250 miles northeast of the city of Edmonton, are centered in an area of something over 12,000 sq mi. The deposit runs as high as 250,000 bbl per acre and the average richness is placed at 100,000 bbl per acre. Of the over 700 billion bbl in place, 400 billion bbl of raw oil are considered recoverable from which 300 billion bbl of upgraded synthetic crude are expected to be produced.' In the deeper zones, thermal stimulation is considered the best approach to recovery, while in the shallow areas several surface mining techniques are deemed practical.

Jan 10, 1972

By Norman B. Braly

The following is not offered as an extended paper on the subject of shaft sinking, but more as a description of the present practice of shaft sinking in the Butte district. The Anaconda company is sinking at present the following shafts: Badger State, Moose, Mountain Consolidated, Mountain View, Pennsylvania and Tropic. At the High Ore and Leonard mines the shafts are being deepened by sinking two compartments and will subsequently be enlarged to the full working size by raising alongside the compartments which are now being sunk. The following other companies are also sinking shafts: Butte-Alex Scott, Butte and Zenith City, Boston and Corbin, North Butte Mining Co. (at the Granite Mountain shaft), East Butte Co. (at the Pittsmont shaft), and the Rainbow Lode Development Co. Shaft Timbering. The shafts of the Butte district, generally speaking, are of three compartments arranged in a straight line, and the pump compartment is usually arranged for the use of an auxiliary hoisting cage, as well as for carrying pipe lines and electric wires. The Rainbow shaft is practically square, and of three compartments. The length of the shafts outside of timber will vary from 17 to 22 ft., and the width from 6 ft. 6 in. to 7 ft. Fir timber is used in all shaft work. This may be obtained from the Coast, when it is known as Coast fir, or from Idaho or Montana, when it is known as native fir. The native fir seems to be the tougher wood, but it is hard to obtain clear lumber in the lengths and sizes necessary for shaft work. Some of the shaft timber of the Anaconda company has been treated with creosote as a preservative, but this practice has not come into general use, as the ground of the camp is so heavy that the timbers usually crush before they rot. The size of timber most used for shaft work is 12 by 12 in., while 10 by 12 in., 10 by 14 in. and 12 by 14 in. are used for some of the special pieces around the shaft. The new Leonard shaft is timbered with 14 by 14 in. wall plates throughout.

Jan 1, 1914

By D. Dever, E. S. Fisher

Measurements of the temperature dependence of the elastic moduli in single crystals of hep ruthenium, rhenium, cobalt, dysprosium, and erbium were carried out for various temperature ranges so as to investigate the correlation, suggested by prior work, between the shear anisotropy ratio, A = C44/C66, and the occurrence of the hcp — bee phase transformation. These measurements confirm the suggestion that A has a positive temperature dependence in that group of hcp metals that undergo thermally induced transfornzations to the bee structure and a negative or zero temperature dependence in the other hcp metals. It appears, from indirect evidence, that the hcp -fee transformation in cobalt is preceded by a highly negative temperature dependence of A. These results indicate that elastic anisotropy is an important factor in determining the temperatures at which martensitic phase transformations occur. Two possible roles for elastic anisotropy are proposed: 1) the shear-modulus ratio within the habit planes must be nearly similar for the two phases and 2) a large anisotropy decreases the stress necessary for the movement of the transfornzation dislocations. FUCHS' calculations of the elastic moduli in the alkali metals have shown that the high shear-anisotropy ratios, c/c', in certain bee metals and alloys are the result of large negative contributions to c' = (c11 - c12)/2 arising from the nearest-neighbor repulsive forces.' On this basis, and following Zener,2 the association between high c/c' ratios and the martensitic phase transformations that occur upon cooling certain bee metals is explained as a unique characteristic of the bee structure. Recent measurements of the elastic moduli in hcp titanium and zirconium show, however, that a high elastic anisotropy also exists in these hcp structures at the temperatures at which they transform to bee upon heating3. If there exists a direct and consistent correlation between the elastic anisotropy in close-packed structures and the occurrence of transformations to the bee phases then there is evidently a need to re-examine the conclusions of Zener theory. Elastic anisotropy may also be the result of the effects of temperature on the stability of the low-temperature close-packed structures or it may play an important role in the mech- anism of the martensitic transformations. The present measurements were aimed at establishing the phenomenological correlation between elastic shear anisotropy in hcp structures and the thermally induced hcp —bee transformations that occur in the majority of the twenty-three hcp metals, as shown in Table I. Prior to the present work the temperature dependence of the anisotropy ratio, A = c44/c66, was known at various temperatures for nine of the metals listed. The data showed a negative temperature dependence of A for cadmium, zinc, magnesium, and cobalt, which do not transform to bee, and a positive temperature dependence of A for thallium, zirconium, titanium, hafnium, and yttrium. The correlation was, however, ambiguous in that these two groups of metals are also separated with respect to the c/a ratios as noted in Table I. There remained the possibility that the temperature dependence of A is a function of c/a and not consistently associated with the transformation. The measurements of the elastic moduli in rhenium and ruthenium, in which hcp —bee transformations do not occur, were needed to help decide this question. The studies of dysprosium and erbium were undertaken to determine whether the correlation holds for the heavy rare earth metals.

Jan 1, 1968

By David W. Brunton

From the old-fashioned " grab-sample " to the modern timing-device, which takes a machine-sample with mathematical precision, there is a wide gap, which was only crossed by many years of toil and unremitting endeavor. Even to-day, notwithstanding the advancement in the art, " grab-sampling " is still practiced—sometimes to afford the unscrupulous mine-promoter a basis for fairy-tales with which to entrap the too-gullible investor, and often by milling and smelting companies to determine the amount of moisture in custom-ores. The latter practice is almost as reprehensible as the former, and it causes more trouble and ill-feeling between seller and buyer than all other factors put together. -NO reputable concern to-day would think of attempting to determine by grab-sampling the amount of gold, silver, lead, or copper contained in an ore, and yet many buyers expect the miner to accept the results of grab-sampling in the determination of the amount of water contained in the ore, forgetting that accurate results are just as necessary here as in the determination of the metals, because the result determines the percentage of weight of the ore which shall be excluded and considered to have no value whatever. Samples for the determination of moisture should be taken with as great care as samples for the determination of metallic content, and in order to avoid the extra expense of a separate operation moisture-samples should be taken from the sample-safe. As the sample reaches the sample-bin in a smaller stream and by a more circuitous route than the " reject" travels in its path to the outgoing car, it loses more moisture en route, and a constant should be added to compensate for this difference. Carefullg ,con ducted experiments have shown that the differ.elice in loss of moisture between the two routes does not exceed 10 per cent. in summer and 7 per cent. in winter. For instance,

Jan 1, 1910

By Tell Ertl

The term oil shale is defined. Foreign oil-shale developments are outlined briefly. The richest and most extensive oil-shale deposits in the United States lie in western Colorado. The Bureau of Mines is opening two adjacent areas for underground mining. in western Colorado. From the first area the oil shale is mined selectively as required by the retorting plant. The second area is being developed as a unit of a full scale oil-shale mine to ascertain the most practical methods of mining oil shale and to determine costs. In both of these mining areas, research will be carried on to develop new and improved practices for mining oil shale. Introduction Oil shale is a sedimentary rock containing a solid mineraloid of indefinite composition known as kerogen. On heating oil shale, the kerogen undergoes thermal decomposition and some of the vapor products of the decomposition can be condensed as shale oil. Oil from shale can be a major source of liquid fuels since extensive deposits of oil shale are known to exist throughout the world. The United States considers the establishment of an oil-shale industry only when doubt exists of the adequacy of the domestic supply of crude petroleum. On the other hand, oil shale is not strange to foreign oil men. The industry is an old one in other parts of the world. The French industry has been in existence since 1838, the Scottish since 1859, the Australian since 1860, the Estonian and Swedish The since World War 1, and the Manchurian industry since 1929. The most highly exploited oil-shale deposits are the Carboniferous shales of Scotland. About 20 seams ranging from 4 to I2 ft in thickness are worked. The yield during recent years in scotland has been 18 to 25 gal of shale oil per ton, from 3&"30'000 tons per year' The French and Swedish oil-shale deposits are of lower grade than the Scottish. The Estonian oil-shale deposits are 7 ft thick, and the oil yield averages 50 gal per ton. Over 1,000,-ooo tons are mined each year, half of which is used directly as fuel to substitute for coal and the other half is used for the production of oil. Immense deposits of oil shale that will yield 10 to 15 gal per ton exist in Germany. Because of the impending loss of the Rumanian and Polish oil fields and the bombing of synthetic liquid fuel plants, the Nazis in 1943 started a large-scale oil-shale program in Germany. By V-E Day, it is said, oil-shale production had reached the rate of 2500 tons per day and rapid expansion of the industry was imminent. Australian oil shale, known as torbanite, occurs in beds 2 to 6 ft thick. It is of a very high grade and on retorting yields 80 to 160 gal per ton. The oil-shale industry of Manchuria was the largest in the world during the past decade. The well-known Fushun coal deposit in Manchuria has an overburden of 500 million tons of oil shale about 450 ft thick that will yield 10 to 15 gal of shale oil per ton. The oil shale is

Jan 1, 1949

By E. M. Wise, T. E. Kihlgren, N. B. Pilling

SYSTEMATIC data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541.

Jan 1, 1935

By Richard F. Moe

INTEREST in developing White Pine, considered since 1942, was renewed by the Korean conflict and its shortage of domestic sources of copper. In view of this Morris F. La Croix, president of Copper Range Co. of Boston, and of its wholly owned subsidiary, White Pine Copper Co., worked an agreement out with Government officials. Essentially the contract called for a construction loan of $57,185,000 at 5 pct interest, with $13 million additional supplied by Copper Range. Defense Materials Procurement Agency contracted for 243,750 tons of copper from the first 275,000 tons produced, at a base price of 25.5& per lb, the contract to expire Dec. 31, 1961.

Jan 4, 1954

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By J. J. Lander, L. H. Germer

Molybdenum and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved onlv limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150°C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1949

By Thomas Wilson

IN a single-crystal cube of iron the arrangement of the atoms is that characteristic of iron at room temperature: the body-centered cubic lattice. X-ray investigation has shown this structure to be characteristic of iron, as it has shown the atomic arrangement of other metals to be characteristic of those metals also. Rarely do substances have more than one characteristic atomic arrangement. Many physical properties of metals are directly connected with their atomic arrangements, so that changes of arrangements produce changes of properties. Only chemical change influences atomic arrangement. If a difference in the physical properties of a metal is caused by a process which involves no chemical change, the cause of the difference in properties must be sought elsewhere than in the atomic arrangement. Frequently this cause can be traced to alteration of crystal orientation. The orientation of a crystal may be defined as the relationship which the crystallographic axes bear to some quantity of reference. A cube of iron appears cubic whether it is regarded from a face, an edge, or a corner. Yet these three positions represent three different orientations of the cube with respect to the observer. It is evident that the orientation of this cube of iron, unlike the atomic arrangement, is not characteristic of iron but is entirely dependent on the previous history of the cube. Most of the processes of metal working, such as wire-drawing, rolling, and bending, change the orientation of the crystals present in the worked metals. These processes usually tend to produce rotation of the crystals into positions approaching a mean. Specimens of metals show-ing this characteristic are said to possess a preferred, orientation. Tensile strength, ductility, and many other properties are influenced by orientation changes; therefore two specimens of the same metal may show different values of these quantities. In metal specimens possessing a narrowly limited preferred orientation, these quantities will vary in magnitude in different directions throughout the specimens. The investigation of the influence of manufacturing operations upon crystal orientation, and hence upon physical properties of metals, is an important

Jan 1, 1929

By Simon Ash

THE coal-mining districts of Washington are mainly west of the Cascade Mountains; Fig. 1. The mines are on the foot hills of the slope, the lignite fields of Lewis and Thurston counties extending into the valleys west of the mountains. An exception is the Roslyn field, a small but important area on the eastern slope. If western Washington is divided into three areas from north to south, the bituminous coal fields and most of the active operations will be found largely in the middle area. The southern portion contains lignites over a large area. In the northern portion, mining is practically restricted to one mine, the Bellingham, which is working a subbituminous coal seam near the city of Bellingham. The degree of alteration that the coal of a particular field has undergone may be gaged roughly by the position of the field with reference to the Cascade Mountains. The lignites of Tenino, Tono, Mendota, and Castle Rock, on the railway line connecting Seattle and Portland, occur in a region, of low relief, in which the Eocene coal measures have suffered only minor disturbances. Subbituminous coals occur in the foot hills, as at Renton, Newcastle, and Bellingham. Coals high in fixed, carbon are found nearer the mountains, where. the measures have been sharply ,tilted and folded, as at Black Diamond and Carbonado. The two typical anthracite fields are located still higher, in the rugged mountains where outcrops appear both in deep gorges and on ridges at elevations approaching 5000 ft. At. Carbonado is found the only semianthracite seam worked on a commercial basis. The occurrence of this seam in a region of bituminous coal is due to the nearness of an igneous sill, which has changed its character from bituminous to semianthracite.

Jan 3, 1925

By K. E. Brown, A. R. Hagedorn

A 1,500-ft experimental well was used to study the pressure gradients occurring during continuous, vertical, two-phase flow through 1-in., 1 1/4-in. and 1 1/3-in. nominal size tubing. The test well was equipped with two gas-lijt valves and four Mathak electronic pressure transmitters as well as with instruments to measure the liquid production rate, air injection rate, temperatures and surface pressures. Tests were conducted for widely varying liquid flow, rates, gas-liquid ratios and liquid viscosities. From these data, an accucrate pressure-depth traverse was construcred for each test in each of the three tubing sizes. From the results of these tests, correlations have beer] developed which allow the accurate prediction of flowing pressure gradients for a wide variety of tubing sizes, flow conditions, and liquid properties. Also. the correlations and equations which are developed satisfy the necessary condition that they reduce to the relationships approprate to single-phase flow when the flow rate of either the gas or the liqutid phase becomes zero. All the correlations involve only dimensionless groups. which is a condition usually Sought for in similarity analysis but not always achieved. The correlations developed in this study have been used to calculate pressure gradients for pipes of larger diameter than those upon which the correlations are based. Comparisons of these calcuclaed gradients with experimetally determined gradients for the same flow conditions obtained from the literature indicate that extrapolation to these larger pipe sizes is possible with a degree of accuracy sufficient for engineering calculations. The extent of this extrapolation can only he determined with additional data from larger pipe diameters. INTRODUCTION The accurate prediction of the pressure drop expected to occur during the multiphase flow of fluids in the flow string of a well is a wideiy recognized problem in the petroleum industry. The problem has been brought even more into prominence with the advent of tubingless or slim-hole completions which use small-diameter tubing. Many of the correlations which give reasonably accurale results in the lager tubing sizes are greatly in error when applied to small-diameter conduits. Small-diameter conduits are defined as 1 1/2-in. nominal size tubing or smaller. The study of the pressure gradients which occur during multiphase flow of fluids in pipes is exceedingly complex because of the large number of variables involved. Further difficulties relate to the possibility of numerous flow regimes of widely varying geometry and mechanism and the instabilities of the fluid interfaces involved. Consequently, a solution to the problem by the approach normally used in classical fluid dynamics based on the formulation and solution of the Navier-Stokes equation has not been forthcoming. This is primarily the result of the nonlincarities involved and the difficulty of adequately describing the boundary conditions. As a result of the foregoing, most investigators have chosen semi-empirical or purely empirical approaches in an efford to obtain a practical solution to the problem. Much of the previous work in this area was done in short-tube models in the laboratory. A number of problems arise, however, when attempts are made to extrapolate these laboratory results to oilfield conditions where a much longer tube is encountered. In those few studies where data taken in long tubes were utilized, the data covered only a limited range of the variables, and as a result inaccuracies are introduced when the correlations are extended outside the range of the original data. Also, as a consequence of the limited amount of data available for these studies, the effects of several important variables were overlooked. The problem of predicting the pressure drop which occurs in multiphase flow differs from that of single-phase flow in that another source of pressure loss is introduced, namely, those pressure losses arising from slippage between the phases. This slippage is a result of the difference between the integrated average linear velocities of the two phases, which in turn is due to the physical properties of the fluids involved. In contrast to single-phase flow. the pressure losses in multiphase flow do not always increase with a decrease in the size of the conduit or an increase in production rate. This is attributed to the presence of the gas phase which tends to slip by the liquid phase without actually contributing to its lift. Many investigators have attempted to correlate both the slippage losses and the friction losses by means of a single energy-loss factor analogous to the one used in the single-phase flow problem. In an approach of this type, hourever, many of the important variables, such as

Jan 1, 1966

By R. E. Cech

Metallographic observations on hydrogen-reduced nickel oxide crystals suggest that nucleation of nickel occurs at structural singularities in the oxide. The fully reduced structure contains micron-diameter, worm-like voids occupying 40 to 50 pct of the volume. The crystallographic orientation relationships between nickel oxide and nickel resulting from oxide reduction are recorded and discussed. THE process of reduction of oxide to metal is one of considerable complexity involving a chemical reduction reaction, mass transport of reducing agent to the point of reaction and of reaction product away from it, and finally a transformation whereby metal atoms released from the oxide rearrange to form a stable reduced phase. In addition, nucleation of the reduced phase affects the overall reaction kinetics. Thus far only the thermodynamic aspect of reduction has received the attention warranted by the importance of

Jan 1, 1960