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By F. A. Forward, A. H. Ross, J. Halpern

Application of the carbonate leaching process to carno-tite ores has often been limited by the difficulty of obtaining simultaneous high recoveries of uranium and vanadium. The chemical aspects of this problem are discussed and the effect of prior roasting procedures on this discovery is described. IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to ±15°C. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO8 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi 02. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1959

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, produced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. 1). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OF THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By H. J. de Haan, J. van Lookeren

In view of their size and favorable characteristics, Shell's heavy-oil fields on the eastern coast of Lake Maracaibo, Venezuela — known as the "Bolivar Coast" — are obvious candidates for the application of thermal recovery methods. During the last decade various methods have been tested, such as steam drive,', steam soak and in-situ combustion.3 Steam soak was discovered as a promising production method rather accidentally in 1969, during early steam drive testing in the Mene Grande Tar Sands1 When steam erupted at the surface due to breakdown of the overburden, the injection wells were back-flowed to relieve the reservoir pressure. This resulted in high oil production rates, all the more impressive because the reservoir is unproducible by primary means. It was concluded that injection of limited amounts of steam might be a very effective method for stimulation of heavy-oil wells. To obtain information that would be more widely applicable, testing of the process was continued in the eastern part of the Tia Juana field (Fig. 1). Here even more favorable results were obtained than in Mene Grande. This created sufficient confidence to prompt a large-scale project, which was considered essential for an adequate evaluation of ultimate recovery, steam requirements, mechanical problems and economic prospects. To obtain an early answer on the ultimate recovery a fairly depleted area was selected in the western part of the same field ("A" in Fig. 1). The first steam was injected in March, 1964. This paper describes the performance until the end of 1966. The production mechanism and well inflow performance are discussed in some detail. In view of the favorable results obtained so far, steam soak operations have expanded considerably since the start of this project. Presently, five other projects are under way, of which two are about the same size as the one under discussion, with further extensions being programmed. Description of the Project Reservoir Data Shell's part of the Main Tia Juana reservoir has a proven area of 8,800 acres and an average net oil sand thickness of 130 ft. It contained an initial quantity of 2,750 million bbl of stock tank oil (STOIIP), with an API gravity ranging from 10 to 15 API and a viscosity of 100 to 10,000 cp (at 122F). As a geological unit it is known locally as the Lower Lagun-illas member of the Lagunillas formation, which is early Miocene in age. The sand bodies are believed to be distributary channel sands deposited in a lower coastal plain. Most of the channel sands have lateral and some vertical communication. The field was developed mainly in the period from 1936 to 1950. The ultimate primary recovery is estimated at 18.1 percent of STOIIP, of which 12.5 percent STOIIP had been produced by the end of 1963 from some 540 wells. By then the average pressure had decreased from an initial value of 960 to 550

Jan 1, 1970

By Frederic P. Dewey

THE Bureau of the Mint of the United States Treasury maintains 13 offices for the purchase of gold-bullion, and this paper describes an investigation to establish the reasonable differences in the assay-results at the various institutions which may be commercially allowable in the settlements between them. Beginning with the comparative assay of proof-gold at the Philadelphia mint and the Utrecht mint, which shows 0.00002 as the closest agreement now possible, eight tables of comparative results, taken from the regular work of the service, are given. These tables begin with very fine gold, produced in an electrolytic refinery, showing close agreement. in the assay-results, and follow through decreasing gold fineness and . increasing amounts and complexity of base metals to very impure and complex bars produced at cyanide-mills, some of which give widely-varying results. Next is given a series of results on samples, prepared and sent out to various laboratories in the service, to test the influence of different metals and various combinations upon the' agreement of the assay-results; 11 samples were sent out and each one was assayed from 44 to 71 times, making a total of 623 assays. To these are added 107 assays of identical samples of coin-gold. On a previous occasion,' I have endeavored to show the degree of accuracy that may be expected in the ordinary everyday analysis of various materials, and on another occasion2 I

Aug 1, 1909

By John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

By C. F., Christopher

The purpose of any steel-making process is to convert the two raw materials iron and scrap into steel. The chemical analysis of the steel is set within certain limits which involve the physical proper- ties desired by the consumer. In addition to tensile properties a large number of other properties are at the present time desired, such as impact resistance, grain size regulation, specific degrees of hardenability, resistance to creep at high temperatures, resistance to expansion on heat treatment, the ability of the product to undergo extreme amounts of cold deformation without failure, and many other properties which are not directly related to the specified chemical analysis. Variations in many of the properties of plain-carbon steels are due to elements and compounds not included in the ordinary "five element"§ composition. Such variations result primarily from variations in oxidation of the metal in the furnace and from the deoxidation method employed. The steel-making problem therefore resolves itself into two distinct sections: (I) the elimination of certain elements from the charge (the iron and scrap entering the furnace) and the addition of materials to meet the chemical specifications for the heat; (2) the manipulation of the slag and metal and the process of deoxidation to give certain desired properties in the steel entirely apart from the chemical analysis specified. Each of &apos;these two ends must be attained

Jan 1, 1957

By J. E. House, C. J. Lewis

In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-pregnant sulfuric acid leach solution is contacted with an organic extractant dispersed in kerosene; the uranium enters the organic phase and associates itself with the organic extractants. Simultaneously an-ions or cations, as the case may be, leave the organic extractant phase and enter the aqueous phase. The two phases are then allowed to separate by virtue of their immiscibility. Based on the data available, a generalized procedure for the recovery of molybdenum from the sodium carbonate scrub liquor of acid leach uranium mills using secondary and tertiary amine extractants is presented, as is another generalized procedure for the recovery of molybdenum from the bleed stream of alkaline leach uranium mill circuits. Such economic appraisal as can be made at this stage of the development is also indicated. Molybdenum occurs in most uranium ores. Whether the uranium is solubilized by the acid leach route or by the alkaline leach process, some of the molybdenum present in the ore is solubilized along with the uranium. Molybdenum in uranium mill pregant solutions may cause processing difficulties, among which may be mentioned the poisoning of resins, the precipitation of organo-molybdenum complexes, or the build-up of molybdenum in recycle streams. While the uranium milling industry has been successful in applying measures to overcome the problems arising from the presence of molybdenum in the circuits, such measures nevertheless add to the cost of producing uranium yellow cake concentrate. Table I shows the analysis of typical uranium pregnant leach solutions. Uranium recovery by solvent extraction is presently practiced only in conjunction with acid leach circuits, and it may be noted that of about 16,000 tons of uranium ore daily processed by sulfuric acid leach, more than half of this tonnage follows the solvent extraction route. Uranium mills leaching ore with sodium carbonate-sodium bicarbonate solution (the so-called alkaline leach circuit) do not use solvent extraction. In this case the uranium pregnant solution is sufficiently pure to permit the direct precipitation of uranium concentrate with subsequent recycle of the alkaline leach solution. While solvent extraction procedures may be developed which are economically attractive for the alkaline leach uranium process, this has so far not been the case. The earlier uranium mill solvent extraction circuits used organo-phosphate extraction reagents, among which di-2-ethylhexyl phosphoric acid was popular. It should be borne in mind that uranium in its sulfuric acid leach solution exists in an equilibrium involving uranium in both anion and cation forms: uo + 2S0 = [uo2(so4)2] For this reason uranium may be extracted by either cation extractors or anion extractors and this is likewise true of molybdenum. However, the organo-phosphate extractants also load ferric iron which is usually present in the uranium acid leach solution. For this reason, it is necessary to reduce this solution substantially to the ferrous state ahead of solvent extraction using organo-phosphate reagents. The amines, being anion extractors, selectively reject iron and thus render the iron reduction step unnecessary. In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-

Jan 1, 1961

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

The income of the Institute is derived mainly from dues, advertising in MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization.

Jan 1, 1939

Jan 1, 1970

By H.A. Bedworth

AlloTs of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry l proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche 3 and Corson. 4 The constitution of the system has also been recently investigated by Matuyama, 5 and in the laboratories of the American Brass Co. by Smith. 6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of the constitution of copper-silicon alloys, the solubility reaches its maximium value, 6.7 per cent. silicon, between 721" and &apos;782" C. At 852" (1. the solubility is 5.25 per cent., while at 400" C. it is only 4.1 per cent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent, silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By H. A. Bedworth

AlloTs of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry l proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche 3 and Corson. 4 The constitution of the system has also been recently investigated by Matuyama, 5 and in the laboratories of the American Brass Co. by Smith. 6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of the constitution of copper-silicon alloys, the solubility reaches its maximium value, 6.7 per cent. silicon, between 721" and &apos;782" C. At 852" (1. the solubility is 5.25 per cent., while at 400" C. it is only 4.1 per cent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent, silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By F. Keller, E. H. Dix, L. A. Willey

The consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathewsi and by Tammann.2 Canlpbell and mathews described principally the beginning of solidification. They found the curve of beginning of solidification rising gradually from the melting point of pure alunlinum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AISb. The curve then drops to the melting point of pure antimony. Tamrriarln explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AISb. The space lattice of the compound AISb, according to Owen and Preaton,³ is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony. The Present Investigation It has been the purpose of this investigation to determine the solid solubility of antimony in aluminum and also to investigate the eutectic temperature and concentration. The experimental work has been carried out in a manner similar to that described in a previous paper4 from this laboratory.

Jan 1, 1931

By Thomas Donnelly

Introduction THE Province of San Cristobal is situated on the south side of the island of Santo Domingo about 25 miles west of Santo Domingo city, the capital of the republic. The copper mineralization is found about 1.-CAMP BUCARO. THE TOP OF THE RIDGE IN THE BACKGROUND MARKS THE CONTACT OF THE LIMESTONE AND TUFFS. S miles north of the town of San Cristobal, in the section known as Bucaro Hill; in San Francisco Hill; on the Nigua River; and on the Jaina (Liver. The district is reached by automobile from Santo Domingo city over an excellent road for 25 miles to San Cristobal, and then, by horse-back 6 or 8 miles up the Nigua River to what is locally known as "Camp

Jan 8, 1915

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors&apos; conclusion.

Jan 1, 1968

By John Chipman, Wayne L. Worrell

Using recent thermodynamic data for the carbides and oxides of tantalum, columbium, and vanadium, the stable solid phases aboue 1300°K and at 1 atm CO(g) pressure in each M-C-O system have been determined. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures necessary to obtain these metals by carbothermic reduction under reduced pressures. TANTALUM, columbium, and vanadium react with carbon to form the M,C and MC carbide phases. The M,C carbides have narrow homogeneity ranges, but the MC phases possess considerable ranges of homogeneity.&apos; The free energies of formation of the MC carbides were recently measured, and those of MC and M2Ccarbides have been estimated., (The notations MC and MC denote, respectively, the carbide compositions at the carbon-rich and at the metal-rich boundaries of the homogeneous MC phase.) In this paper, these carbide data are combined with thermodynamic data for the oxides to predict the stable phases in the Ta-C-O, Cb-C-O, and V-C-O systems at specified temperatures and oxygen pressures. M-C-O PHASE DIAGRAMS The solid phases in equilibrium above 1300°K for each M-C-0 system are shown in Figs. 1, 2, and 3. Above 1300°K, the vapor would consist entirely of carbon monoxide; and these phase diagrams were obtained by specifying the vapor pressure of CO(g) to be 1 atm. The temperature at which any two solid phases become unstable is specified along the two-phase equilibrium lines in each diagram. To simplify the diagrams, all solid phases in the Ta-C-O and Cb-C-O systems are represented as stoichiometric compounds. However, the homogeneity ranges of VO and VC are indicated, because they form a complete series of solid solutions.3 It also should be noted that the homogeneity range of

Jan 1, 1964