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By Wilbur C. Helt

The United States is self-sufficient in bituminous coal and lignite resources to meet the high range of energy demands forecast for the remainder of this century and beyond. The known or proved recoverable reserves of energy from coal in the United States are estimated to be 88% of all fuel reserves, whereas the energy reserves for oil are estimated to be 276, gas 376, shale oil 5% and uranium 2% (as now used). The demand for all forms of energy used in the United States is increasing at a rate of 3% to 4% per year. Presently, coal is competitive on a supply and cost basis with other fuels in conversion to electrical energy and as a source of energy for converting raw minerals to metals and nonmetals, but it is not competitive in transportation and other uses that demand the high flexibility that oil and gas enjoy because of their form. Coal conversion to fluid forms is essential to make it interchangeable with gas and oil to meet the markets they now occupy. Essentially, the chemical constituents that make up coal are the same hydrocarbons that make up oil and gas; it is a matter of reconstituting the proportions of hydrocarbons to make coal interchangeable with the other fuels. The production of coal has fluctuated widely between the peak production of 631 million tons in 1947 to a low of 403 million tons in 1961. Throughout this period, the total value of the production, f.o.b. mines, has averaged more than $2 billion annually. Beginning with 1962, there has been a steady upward trend in coal production with only minor fluctuations that were mainly caused by labor disputes. Output for the latest typical year, 1970, was 588 million tons. Production in 1971 was affected by a major strike and dropped to 548 million tons. Exports of coal from United States to foreign countries have increased steadily and developed into a substantial annual market for over 71 million tons per year. About 56 million tons of this is suitable for metallurgical purposes, and the remaining 15 million tons is exported for electric power generation. The largest single-industry demand for coal is in the electric generating industry, Fig.1. Roughly, the production of electricity has doubled every

Jan 1, 1973

By John A. Putnam, Morrough P. O’Brien

DATA on the physical and thermodynamic properties of hydrocarbons have been made available in recent years but the formal method of applying these data to flow in porous media appears not to have been fully developed. By making usual thermodynamic assumptions and employing existing data on permeability to two-phase flow, Darcy's law may be applied to obtain the flow characteristics for representative combinations of flowing medium and geometry. The numerical examples presented herein are based on hydrocarbons for which complete physical and thermodynamic data are available under equilibrium conditions. INTRODUCTION Thermodynamic data are obtained in the laboratory under equilibrium conditions and their application requires the assumption that equilibrium also exists during flow. This assumption is at least usual in engineering analyses, though not easily justified in many instances, and will be followed here. In regard to hydrocarbons, laboratory experience in determining the pressure-volume-temperature relationships indicates that gas-liquid mixtures must often be stirred vigorously for periods of 15 to 20 min. before reaching equilibrium. On the other hand, boiling and condensation are known to occur on solid surfaces and the large surface exposed to the flowing substance by a porous medium may bring about rapid approach to equilibrium. For the purpose of providing at least a guide to experimentation and a standard for later comparison with experimental results, it will be assumed that the phases present in cross sections perpendicular to the direction of flow are in thermodynamic equilibrium. Another assumption usually made in the solution of problems of flow in porous media is that the fluid remains at a constant temperature; i.e., isothermal flow. This assumption is arrived at by considering the porous medium and surroundings to be an infinite heat source and the rate of heat flow to be infinite at a boiling front. Its validity depends in large measure upon the character of flow, the number of components, and the physical and thermodynamic properties of the fluid. However, the assumption of isothermal flow represents a limiting case. The other limit can be represented by the assumption that the fluid is thermally isolated; i.e., irreversible adiabatic. The thermodynamic process characterizing the actual flow of a given fluid system probably lies somewhere between these two limiting cases and might be thought of as a flow system in which the confining walls are maintained at a constant temperature. For isothermal flow the solid material of the porous media is considered as the infinite heat source capable, without loss in temperature, of giving up heat to the fluid as the latter tends to cool by expansion. For the thermally isolated system, the solid material is considered to give up no heat to the fluid. In the intermediate case the impervious walls confining the porous media are at constant temperature from which heat is transferred along various paths, solid and fluid, throughout the porous media. It would appear that an actual petroleum-

Jan 1, 1941

By R. V. Wheeler, W. Francis

Of the methods that have been used for studying the chemical composition of coal, attack by reagents has not, in general, yielded much information. Most of the reagents used have been strong oxidants such as nitric acid or Schulze's solution. The use of a milder oxidizing agent, such as air at low temperatures, enables progressive changes in the character af the coal substance to be studied and thus helps toward an understanding of its constitution. British bituminous coals frequently have a banded structure. These bands (of four types) can be separated one from another and have been found to possess markedly different chemical characteristics, even when taken from contiguous portions of the same lump coal. It has been found convenient to give each of the ingredients of banded coal a distinctive name, more or less descriptive of its appearance, and the study of the chemistry of bituminous "coal" in England has resolved itself into a study of each ingredient separately. The coal chosen for this work was taken from the Top Hard seam at East Kirkby colliery, Nottinghamshire, a detailed chemical analysis of which has been recorded by Baranov and Francis.' The banded structure was well marked and the bands could readily be separated. The research was confined to the brilliant vitreous bands (vitrain), the dull hard bands (durain) and the "sooty partings" main); for previous work had shown that the fourth type, to which the name clarain has been given, is intermediate in character, chemically, between vitrain and durain. The method of experiment was, briefly, to draw a slow current of moist air through weighed samples (50 gm.) of the three ingredients, vitrain, durain, and fusain, in the form of powder (through a 60-mesh and on a 90-mesh sieve) contained in glass tubes which could be maintained at a constant temperature during prolonged periods. After passing through the coal, the air bubbled into a measured volume of

Jan 1, 1925

By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By E. N. Mazza, H. S. Kalish

The effect of sintering types 302, 3028, and 430 stainless steel powder compacts in hydrogen and dissociated ammonia was investigated. It was found that sintering in dissociated ammonia resulted in as much as 0.5 wt pct increase in the nitrogen content of stainless steel even though the dissociation of the gas was complete. Sintering in hydrogen, on the other hand, reduced the nitrogen content of the stainless steel to less than 0.01 wt pct. In the case of the 302-type stainless steel, the low nitrogen content resulted in a material that was largely ferritic, whereas the high nitrogen content rendered the material fully austenitic. Sintering in dissociated ammonia resulted in lower density, generally lower tensile strength, less ductility, and higher hardness than sintering under equivalent conditions in hydrogen. The reduction of oxides on both stainless steel and iron particles was found to be effected by hydrogen partial pressure in the sintering atmosphere. Compacting pressure was found also to effect oxide reduction during sintering. DISSOCIATED ammonia often is used as a substitute'.' for hydrogen in sintering and in annealing, since economic advantages sometimes can be obtained by such a substitution. In addition, anhydrous ammonia contains very little impurity. Thus, dissociated ammonia gas is very dry whereas tank hydrogen often must be freed of oxygen and water vapor prior to use in many applications. The sintering of stainless steel powder compacts as well as bright annealing is well recognized as requiring a hydrogen atmosphere and for the foregoing reasons dissociated ammonia is frequently substituted. It has generally been overlooked, however, that the nitrogen in dissociated ammonia might have an important effect on the sintering process and on the properties of stainless steel compacts. Considered an inert gas in many applications, nitrogen, on the other hand, is very reactive with cer- tain metals. Dissociated ammonia could not be used for hydriding zirconium or titanium. Nitrogen reacts with columbium, tantalum, chromium, uranium, thorium, and many other active metals. Iron and iron-base alloys are, for the most part, inert in nitrogen but there are many borderline cases. It has been reported that stainless steel stabilized with columbium or titanium should not be sintered in dissociated ammonia.3 olybdenum has been reported as reacting with dissociated ammonia to a minor extent.' Although most of the reactions with iron-base alloys are attributed to the action of un-dissociated ammonia and the action of nascent nitrogen, Uhlig4 showed how readily pure molecular nitrogen reacts with and diffuses into 18-8 stainless steel at 1150°C. He also pointed out how readily nitrogen diffuses out of 18-8 stainless steel when heated in pure dry hydrogen, and these thorough investigations on the subject show that commercial stainless steels are nitrogen-bearing, since they are melted in air. The effects of nitrogen in stainless steel, particularly the 18-8 Cr-Ni type, previously have received considerable attention." In 1926, it was pointed out

Jan 1, 1956

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By V. Carlson, J. A. Rowe, E. O. Bennett

This report concerns the microbial flora found throughout the surface facilities of six water-injection systems in Texas and Oklahoma. Each system is described in detail and water quality data are presented when available. Pseudomonads and sulfate-reducers (Desulfovibrio) were the predominate organisms found in the systems. The genera Sphaerotilus, Bacillus, Achromobacter, Minococcus, Clostridium, Flavobacteriurn, and Sarcina were also isolated in significant numbers. Molds, iron bacteria, sulfur bacteria and soil bacteria were found less frequently in the systems. It is concluded that a complex microbiological flora exists in oilfield water-injection systems. A tendency for waters to deteriorate in passage through solid bed filters is also noted. INTRODUCTION The injection of water into a subsurface formation is often accompanied by numerous problems, the origin and nature of which are only partially understood. During the past few years, investigators have indicated that bacteria are involved in some of these problems even though very little specific information is available concerning this matter. It is surprising that investigators working on microbiological problems in water injection have never made a complete study of the flora of these systems. The logical course to pursue is that of identifying the microbial flora and then examining each organism individually and in combination with others to determine if they produce a particular problem. The objective of the present investigation is to identify the microbial flora in water-injection systems. In addition. the quality of the water in most of the systems was determined and some observations made on the extent to which passage through surface-handling facilities affects water quality. The information derived from this study can serve as a foundation for additional basic investigations. EXPERIMENTAL PROCEDURE The microbial flora of six water-injection systems were studied at 50 sampling points. These systems are experiencing problems which may be attributable to micro-organisms, and two were being treated with antimicrobial agents at the time of this study. The samples were obtained by inoculating 1.0 ml of the water onto the different media at the sampling point. The media used for primary isolation included nutrient agar, Strokes agar, M-10-E medium and semi-solid thioglycollate medium. The cultures were returned to the laboratory, incubated at 30°C until growth occured; then, pure cultures were obtained from individual colonies. The pure cultures were identified according to standardbacteriologica1 procedures. Those organisms not fitting identification criteria exactly, even though exhibiting close similarities to known species, are listed as unidentified organisms. Membrane filters were used to make water-quality tests at intervals before and after collection of the microbiological samples. The filter discs were 47 mm in diameter with a 0.45-micron particle-size retention, and the tests were done under closed conditions at 20) psi. Membrane flow rates are plotted as increasing filtrate volumes, and the total solids contents arcs given when available. An effort was made to sample at each place in a system where a change in environment occurred. In this manner, the effect of passage through filters, tanks, hay sections, etc., on the microbial flora and water quality could be observed. RESULTS SYSTEM A This waterflood system (Fig. 1) is about four years old and daily pumps approx&ately 110,000 bbl of oil-free sour water from a 3,700-ft deep reef. The

By Leon Merker

FLAME fusion growth of strontium titanate crystals was undertaken to obtain large transparent crystals on which physical data could be gathered. The fact that strontium titanate is a cubic crystal and probably has a high index of refraction indicated that it might be useful in optics. No large boules* of strontium titanate had been synthesized previously, and none have been found as natural occurrences. The flame fusion process, invented by Verneuil in 1904,1 was first applied to grow large crystals of ruby and has since been used extensively to grow crystals of corundum and spinel on a commercial scale. Only during the past nine years has this technique been applied to the growth of large single crystals of other high melting compounds such as rutile,2 mullite,3 and ferrites4 One of several significant advantages of the flame fusion technique over more conventional methods of growing crystals from a melt is that the crystals are grown without the use of melt containers. This fact alone excludes other methods of growing crystals from a melt whenever there are compounds with a melting point near 2000°C or above. Growth of the crystal, similar to that of a stalagmite, takes place inside a circular refractory furnace that does not contact the crystal, Fig. 1. This eliminates a serious source of impurities as well as the likelihood of multi-crystalline solidification along the container walls. The flame fusion technique is particularly advantageous for research because it produces large crystals quickly and at lower cost. A corundum crystal 25 mm long and 12 mm in diam can be grown in 2 to 3 hr. Operating conditions permit observation of the growing crystal during any stage of the process. The various flame patterns and a wide range of oxidation-reduction conditions can be investigated in a relatively short time. It should be pointed out that formation of the foot of the boule is the most critical step in growing an unfractured boule. When the tip of the sintered cone is fused to initiate crystal growth, the original area of fusion should be kept as small as possible so that one crystallite can assume dominance over all the others and propagate as a single crystal. If the boule start happens to consist of several crystals, usually the entire boule also contains several crystals. In many cases these tightly cohering crystals exhibit different crystallographic orientations. Although the basic technique of the original Verneuil process has been retained, refinements in method and burner design have been developed in recent years. For example, boule growth may be initiated on a seed crystal rather than by fusion of a sintered cone. The danger of multicrystalline or twinned boule starts is thus eliminated, and this procedure may also be used to grow boules of predetermined crystallographic orientation. Prior Art: Of the many attempts to produce artificial gem crystals, most early efforts% ere directed toward synthesis of .rubies and sapphires and diamonds. None of these efforts resulted in a process that was commercially practical. Without exception only tiny crystals of corundum were obtained, and those at excessive cost. Verneuil announced his process in 1904; Ravier6 in 1934 presented a detailed description of a commercial boule production plant. Descriptions of the German synthetic stone industry, the process details, and the equipment used have been published by Barnes7 and by Merker.'

Jan 1, 1956

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By Fred H. Poettmann, J. K. Welchon, A. F. Bertuzzi

A series of gas-lift tests was made which verified conclusions reached from previous studies and which showed that gas-lift performance could be calculated if reasonably accurate data on the producing characteristics of the well are available.' The test installation is described. Its essential features consisted of a rate-of-flow controller to regulate the input gas and an auxiliary string of small diameter tubing to conduct the input gas to the point of injection in the eductor tubing. In general, it was shown that for continuous gas-lift operation, injection should be as deep as possible consistent with available gas pressure and rate of production desired. Calculated curves are presented which completely characterize the gas-lift performance of the well tested. INTRODUCTION A correlation based on field data from a large number of flowing and gas-lift wells, covering a wide range of oper- ating conditions, was developed which permitted the logical design and prediction of the performance of continuous gaslift installations.' The procedure made it possible to calculate the depth, pressure, rate at which to inject gas, horsepower requirements, and the effect of production rate and tubing size on these quantities. As a result of these calculations certain significant facts were brought to light or re-emphasized. The presence of efficient ranges of operation and an optimum injection depth for a given rate of production were shown to exist as well as the fact that the lower the tubing pressure the less the horsepower requirements to lift the reservoir fluids. The fact that the gas lift performance can be predicted by calculation does not mean that any given installation will perform over the entire range predicted. Many of the conventional continuous gas-lift installations will not permit operation over the entire range predicted by calculation (particularly in the efficient range of operation) because of the performance characteristics of the installation. Consequently, field tests were initiated for the purpose of investigating and arriving at a simple continuous gas-lift installation which would operate under all conditions predicted by calculation. The first series of tests involved the use of mechanically operated valves. These valves were slip-joint type valves which are opened and closed by lowering or raising the tubing at the surface by means of a hydraulic jack. These valves were chosen because it was hoped that they could be opened or closed at will and did not depend on the gas pressure in the annulus or the pressure of the fluid in the tubing for their operation. Unfortunately, the valves did not operate satisfactorily and it was imossible to open or close each valve at will. Some limited data were obtained, however, which verified the predicted benefits resulting from the use of lower tubing pressures. In the next series of tests the valves were removed and the gas was injected from the annulus through a 14/64-in. orifice equipped with a reverse check valve. A packer was set below the valve to seal off the space between the 2-in. tubing and 5-in. casing. The injection point was located at 3,810 ft. This arrangement provided satisfactory mechanical operation. However, it was impossible to obtain low rates of liquid production at low tubing pressures as predicted by calculation. A minimum gas injection rate existed below which steady flow was impossible. Liquid pro-

Jan 1, 1953

By Gerald C. Mathis

FERGUS County, Mont., shown in Fig. 1, is known for its once famous gold mines near the old towns of Gilt Edge, Maiden, and Kendall. But at Heath, a small farming community near the foothills of the Snowy Mountains, thousands of tons of gypsum have been mined since 1916. The value of the gold taken from the mines of Fergus County runs into millions of dollars; the value of the products made from the gypsum of the Heath mine is also in the millions. The gypsum mine will continue to produce for many years, while the gold mines are closed today. The Heath gypsum mine was developed by the Northwest Gypsum Co. in 1916. The products of the small mill built by this company were plaster, agricultural gypsum, and raw gypsum for cement manufacturing. The United States Gypsum Co. prospected the adjacent property in 1916 and 1917 by means of two adits and some exploration drill holes. During World War I, the company abandoned operations at Heath, but again became active in this area in 1928 hen it purchased all the property of the Northwest Gypsum Co. A long range program of expansion was begun with the building of a block plant and the purchase of additional land and mineral rights. A modern wall board plant was built in 1936. When the old wooden mill purchased from the Northwest Gypsum Co. burned in 1937, an all-metal calcining plant located at Blue Rapids, Kansas, was dismantled, moved to Heath, and erected on the site of the mill. In August 1951 a new mine was opened 3000 ft north of the mill. Rock is conveyed from the mine to the mill by an 18-in. belt conveyor. The Heath gypsum deposit lies at the base of the Ellis formation of Jurassic Age. The Ellis at Heath lies unconformably on the black fissle shale of the Heath formation of the Big Snowy Group, which is Mississippian in age. The strike of the gypsum bed is N45°E and the dip approximately 3" NW; the regional strike and dip of the area. The gypsum lies in a series of six layers separated from each other by thin seams of shale. The lower layer is composed of' gypsum and shale intermingled and is not of commercial grade. The upper five layers are high in purity, but only the middle four layers are mined on the advance, as the top layer is left for roof support. This top layer is mined on retreating operations at the same time the pillars are robbed. Total thickness of the gypsum layers varies from 12 to 14 ft. Fig. 2 shows the average thickness and arrangement of the layers. Mining Methods The mine was originally developed by driving an adit into the gypsum horizon. The Northwest Gypsum Co. mined in the top four layers, the top layer being split, leaving about 12 in. for roof support. A modified room and pillar method was used: entries were 15 ft wide and rooms varied between 20 and 30 ft and were turned on 90" from the entries. Crosscuts between the rooms left pillars from 10 to 20 ft square. The rock was loaded by hand into 1-ton mine cars and pulled to a central gathering point by mules; from the gathering point, mules or horses were used to pull the string of cars to the mill tipple. This method was continued by the United States Gypsum Co. from 1928 to 1937.

Jan 1, 1954

By A. S. Appleton, M. B. Bever

The stored and expended energies of an Au-Ag alloy deformed in torsion were investigated as functions of strain, strain rate, and temperature. At room temperature, the stored energy, measured by tin solution calorimetry, increased linearly up to an intermediate strain, above which it was nearly constant; at 78 °K the relation was linear up to fracture. Approximate values of the energy stored at 4 OK indicate a rapid increase below 78 OK. The energy stored by specimens deformed successively at 4o and 78oK changed slowly with increasing second strain from the curve for energy stored at 4 OK (measured after annealing at 78oK) to that for deformation at 78°K. The ratios of the stored to the expended energy at room temperature and 78 oK were unusually large. The additional amount of energy stored at the lower temperature is attributed mainly to an increase in the number and energy of dislocations. The stored energy as a function of strain rate at 4oK (measured after annealing at 78oK) increased to a sharp maximum over a narrow range of strain rates, whereas the expended energy changed only slightly. These effects are explained by the generation of point defects resulting from the enforced nonconservative movement of jogs in fast moving screw dislocations. The effect of straining successively at two strain rates at 4oK was also investigated. Stress-strain curves for 4o, 78oK, and room temperature and the results of micro examination of specimens deformed at these temperatures are also reported. THIS investigation is a continuation of a research program primarily concerned with the effects of variables on the energy relations involved in the deformation of metals. The variables investigated in earlier work have included strain, strain rate, temperature of deformation (room temperature and 78oK), and the type of deformation process. Most of this work has been carried out with Au-Ag alloys. In the investigation reported here, the deformation process was torsion, which had not been used previously in the program. The stored and expended energies involved in the deformation process were measured as functions of strain, strain rate and the temperature of deformation in the range 4" to 373" K. The microhardness and microstructure of deformed specimens were also investigated. The relation between stored energy and strain differs for different deformation processes.1,2 In general, the stored energy increases with strain and may attain a nearly constant value at large strains. This value and the rate at which it is reached, however, depend on the process of deformation. This dependence has been attributed, at least in part, to differences in the effective strain rate and rise in temperature of the specimen during deformation. The effects of the temperature of deformation on both the stored energy and the energy expended in the working process have been the subject of only a few investigations.3-6 Values of these quantities at low temperatures are of special interest as they yield information on point defects which, for many metals, is not obtainable at higher temperatures. The effect of the strain rate on the stored and expended energies has received little attention The strain rate has usually been measured only in relative terms, and hence the interpretation of its effect on the stored energy has been mainly comparative.

Jan 1, 1963

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By R. L. Dietrich

[ ] We at The Dow Chemical Co. have recently done some work on the deformation of magnesium alloys and although it is far from complete there have been a few observations which may be of interest in connection with this paper. In the first place, I should like to point out that the deformation of polycrystalline magnesium alloys has not been completely explained by the work on single crystals. Bakarian and Mathewson found slip on the ( 101) and {002) planes, and (102) twinning as the deformation mechanisms in magnesium single crystals, but in compression when the (002} planes were within ii° of parallel t0 the compression surfaces, fracture occurred at all temperatures up to 340°C (644°F). In commercial working processes, particularly in rolling, an orientation is quickly produced which should be unfavorable to further deformation by the three established mechanisms. The first few reductions in rolling quickly produce an orientation having

Jan 1, 1947

By R. S. Archer

THE binary aluminum-silicon alloys have certain characteristic advantages which are now well known, and these alloys have come into considerable use during the past several years.1 Their field of application has been limited to a certain extent, however, by their low yield point and hardness, low endurance limit, and relatively poor machining characteristics. These properties are improved by the addition of copper, and the ternary aluminum-silicon-copper alloys constitute an important class. The addition of copper decreases the corrosion resistance of the aluminum-silicon alloys and increases specific gravity. Magnesium is a hardening addition which seems to have relatively little effect on corrosion resistance, and which, of course, reduces specific gravity. The object of the work described in this paper was the development of alloys and heat treatments for the production of sand castings and permanent-mold castings having substantially all the advantages of the binary aluminum-silicon alloys together with mechanical properties improved to a degree permitting wider application.

Jan 1, 1930

NEW MEMBERS The following list comprises the names of those persons who became members during the period of Nov. 10, 1917, to Dec. 10, 1917. ADAMS, LLOYD D Supt., Hoskins Mine, Mineral Point Zinc Co., Galena, Ill. ARMSTRONG, WILLIAM D., Min. Engr.. Empire Coal Co., 715 American Trust Bldg., Birmingham, Ala. BALL, TOM LEE, Efficiency Engr., Iron Mines Dept., Tennessee Coal, Iron &.R. R. Co., Bessemer, Ala. BENZIE, WILLIAM ROSE, Sec. & Treas., The Republic Coal Co., 901-2 Foster Bldg.,Denver, Colo. BERGSTROM, GUNNAR, Min. Engr.... Resident Mgr., Russian Dept., Swedish Diamond Rock Drilling Co., Slatawostowskaja Ulitza 6, Ekaterinburg, Russia. CADOT, J., Engr.,. Hardinge Conical Mill Co., Newhouse Bldg., Salt Lake City, Utah. COFFEY, GEORGE W 64 Santa Clara Ave., Oakland, Cal. CUTLER, WILLARD WALKER, JR Geol., Carter Oil Co., Tulsa, Okla.' . DANIEL, JOSEPH A., Min. Engr. & Geol., Hudson's Bay Co., Care The Institution of Mining & Metallurgy, 1 Finsbury Circus, London, E. C., England. EARDLEY, WALTER HAZEN, Cons. Engr., Chanute Spelter Co., 316 Frisco Bldg Joplin, Mo.

Jan 1, 1918

By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).' A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;' however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By T. M. Olson, B. G. Lewis

The adsorption of selenite on bentonite, kaolinite, and an iron--coated illite was studied to determine the importance of several soil variables on selenite removal from uranium mill tailings pond seepage. Adsorption capacities of the clays of selenite varied by orders of magnitude and decreased in the following order: illite > kaolinite > bentonite. Maximum adsorption of selenite on the clays was observed between pH 2.5 and the clay's zero-point-of-charge. Substantially less selenite was adsorbed on these clays in actual mill tailings solutions than in model systems. Virtually all selenite was removed from the tailings at pH 7. The principal removal mechanism at this pH is suggested to be the adsorption of selenite on freshly precipitated metal hydroxides. It is concluded that selenite can be removed from tailings seepage in soil or in clay liners in the presence of kaolinitic clays and iron oxides. Selenite would also tend to be removed from tailings seepage in calcareous strata.

Jan 1, 1984