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By A. H. Daane, J. F. Haefling

BECAUSE of the wide use of platinum in industry and research, the physical properties of this metal, including its vapor pressure, have been studied in some detail.' The other members of the palladium-platinum group of metals have not been studied as extensively, and only qualitative information is available on the vapor pressure of palladium. Data given in literature by Vines1 and Brewer2 on the vapor pressure of palladium are based on the qualitative observations by Holborn and Austin3 and Crookes4 on the rate of volatilization of palladium filaments in various atmospheres. The general observation that palladium is the most volatile metal of the palladium-platinum metal group was corroborated by Bell, Love and Normand who studied the separation of isotopes of the platinum-group metals by a mass spectrometric method. We have measured the vapor pressure of palladium using the Knudsen effusion technique. In this work, the effusion vessel was suspended from a quartz-fiber microbalance into an induction furnace, and the amount of vapor effusing from the vessel was determined by direct weighing of the vessel during the measured heating times. This technique has been described in a report from this laboratory." The vapor pressure of palladium was calculated from these measurements using the equation P...... = 17.14 -W- (77m)'u [1] a t where ? is the weight loss in grams of vapor of molecular weight m from a vessel having an orifice of a sq cm, during t sec. The derivation of this equation from kinetic theory has been described in a previous report from this laboratory: as well as in texts discussing the kinetic theory of gases.%" Test Vessel—In the search for a suitable material for the effusion vessel, it was found that tantalum reacted with palladium metal to form intermetallic compounds, and graphite was readily dissolved in palladium metal to form what appeared to be a liquid phase at a temperature several hundred degrees below the melting point of palladium. On cooling, the graphite gathered into spherical balls in the palladium, with crystals extending radially from the center of these balls, some of which were a millimeter or more in diameter. However, palladium metal vapor did not attack the graphite vessel, so graphite could be used where it did not contact condensed palladium. Tungsten did not appear to react with palladium vapor or molten palladium at its melting point, but it was not convenient to use a tungsten-vapor pressure vessel because of the difficulty of fabricating this metal. Since the vapor-pressure range to be studied (10 2 to 10 ' mm) did not appear to extend above the melting point of palladium, a combination of tungsten and graphite served to provide a very satisfactory effusion vessel. The lower half of the graphite vessel was lined with some strips of tungsten foil and the sample of palladium consisting of a coil of sheet was placed in the tungsten liner; in this way, no contamination of the palladium by carbon occurred. Procedure After outgassing at 1500C, the tungsten-lined graphite effusion vessel was loaded with 300 mg of

Jan 1, 1959

By N. A. Rose, E. L. Spain

THIS study was undertaken primarily to determine the reasons for certain variations in the soundness of gravel aggregate taken from a number of widely separated points on the Tennessee River. Under laboratory tests, concrete made with these various aggregates in some cases exhibited marked differences in specific gravity crushing strength and durability. Gravel was studied in detail from Chattanooga to the mouth of the river and to a lesser extent from Chattanooga to Knoxville. The causes of variation were determined, and variational curves were constructed, which accurately predict the composition of aggregate at any point on the river and therefore its relative suitability for use in concrete. The aggregate at any point is suited for making sound concrete; the variance of suitability is due to varying percentages of sandstone and weathered material, which are less sound than other constituents. INTRODUCTION When it is stated that the aggregate from one point is inferior to that from another, it must not be construed to mean that the gravel is unfit for use. The classification upon which such aggregate ratings are based is largely arbitrary, thus inferiority or superiority is merely relative. Samples of gravel were selected from stockpiles at the dams of the Tennessee Valley Authority under construction, from the stockpiles of private companies along the river, and from samples taken by the gravel- exploration barge of the T. V. A. One hundred or more gravels of each size studied were selected at random by taking small handfulls while walking around the piles. These were separated according to the different mineral or rock constituents present, and the percentage of each constituent was obtained by counting. At least three such samples were taken from each size, and all checked with one another within a few per cent. The results were then averaged. In order to check on the accuracy of such sampling, a whole sample was taken from one point after the gravel was thoroughly mixed. The two methods gave approximately identical results. SOURCES AND TYPES OF MATERIALS The sources of gravel found in the Tennessee River are numerous and varied. The river itself traverses several geologic provinces, each

Jan 1, 1937

By J. H. Hollomon, J. C. Fisher

THE fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actual and the theoretically computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commercially available materials. Computations have been made1, 2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most important of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect concerns the relation between deformation and the stress required for fracture. Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior compressive deformation. This marked anisotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffé, et a13 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence of the measured fracture stress from the theoretical value, the size effect, and the effect of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the element of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only does the magnitude of the fracture stress depend upon the size and shape of these particles, but also its dependence upon strain is affected by changes in shape and size of the particles. The precipitate resulting from the age hardening of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends on the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrated by Griffith4 to arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of sufficient magnitude to raise the stress at this location to a value comparable with the theoretical strength of the material. If the cracks were reduced in size, Griffith showed that the observed fracture strength increased by virtue of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

By C. Burton Clark, J. Spotts McDowell

Refractories are defined as "materials having the ability to retain their physical shapes and chemical identities when subjected to high temperatures," or as "nonmetallic materials suitable for the construction or lining of furnaces operated at high temperatures." While resistance to "high" temperatures is thus the primary requirement for refractory materials, it is by no means the sole requirement. They must be able to withstand thermal shock resulting from rapid heating or cooling; other stresses induced by temperature change; pressures from the weights of furnace parts or contents; mechanical wear (abrasion) resulting from movement of furnace contents; and chemical attack by heated solids, liquids, or gases. Refractories of many kinds are needed for the many and widely diversified industrial applications. Those in greatest demand are classified on the basis of composition or properties into a few main groups, known as alumina-silica, silica, basic and insulating refractories. In each of these groups there are several classes. In addition to those included in the main groups, there are various special refractories, including silicon carbide, carbon, zircon, zirconia, alumina, and several others. Alumina-silica refractories comprise two main divisions: fire clay and high-alumina. The alumina content of fire-clay refractories covers the range from about 45 pct to 18 pct, and the silica content from 50 pct to 80 pct. The alumina content of fired high-alumina refractories ranges from about 99 pct to 45 pct, and the silica content from about 0.5 pct to 50 pct. Silica refractories of the different classes contain 94 pct to 97 pct silica. Basic refractories include periclase (magnesite), chrome spinel, forsterite, and dolomite. Refractory materials, including insulating firebrick, are supplied mainly as preformed shapes. Other products include bonding mortars and high temperature cements, ramming mixtures, plastic firebrick, hydraulic setting castables, dead-burned grain magnesite, and dead-burned dolomite. Refractory brick are classified on the basis of their physical form as Standard Sizes and Special Shapes. The Standard Sizes are brick of certain definite sizes and relatively simple design which are used in sufficient amounts to permit quantity production. The brick most widely used are the standard 9 in. X 4 ½ in. X 2 ½in. and 9 in. X 4½in. X 3 in. straights and corresponding series of sizes. All brick of nonstandard dimensions are regarded as "special shapes." They include a wide variety of brick regularly used for specific services, such as baffle tile for boilers, checker brick for regenerators, and others; together with shapes of special design manufactured on particular orders from designs submitted by the user. Not included in the broad classifications of Standard Sizes and Special Shapes are several specific-service refractory products, usually made by companies which specialize in their manufacture, or in some cases by the consumers themselves. These products include

Jan 1, 1960

By Kenneth C. Vincent, A. M. Gaudin

IN a study1of the action of amyl xanthate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form 1 then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleachable xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete monomolecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene solution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral-a phenomenon that was totally unexpected yet remains interesting and perhaps important. METHOD OF RADIOACTIVE SPIES The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by Pollard and Davidson.3 The method was first developed by Von Hevesy and Paneth in 1913, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method. A fundamental tenet of the method is that a radioactive atom and a nonradioactive atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1944

By J. C. McCarthy, J. B. Stone

AT Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. LOCATION The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in the world. Another famous old silver district, Sombrerete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo station on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proa[n]o hill are the Fresnillo mines, and it is marked now by a great gash cut by gloryhole mining. HISTORY According to an account written in 1834 by Francisco García, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between Zacatecas and Sombrerete. Little is known of the earliest mining at Fresnillo. which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notable active in 1751 under an administrator named Murguía, who left detailed notes describing them. In 1757, however, the mines became inactive because of difficulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor García had been aroused by the long disregarded notes of Murguía. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difficulties, including abnormal rains and an epidemic of cholera. In 1833 English capital was sought to allow installation of steam-driven Cornish pumps at the two principal shafts and to build the great hacienda de benefacio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1942

By H. M. Chance

(Butte Meeting, August, 1913.) ADEQUATE treatment of the difficulties surrounding the valuation of mineral lands requires that agreement be first reached defining value as understood for the purpose of appraisal. To define value as the price of a product is not sufficient, and does not assist us in using the factors that cause variations in values and in relative values. The real value of any product depends primarily upon its relation to the necessities, comforts and pleasures of mankind. As the necessities, comforts and pleasures of the civilized races differ from those of more primitive man, the value of products varies with the degree of civilization and the environment of the consumer. Coal has no value to the savages of warm climates, and arrow-head flint none to the residents of New York. It has long been recognized that what has been termed ? intrinsic value " must be limited to materials that are essential to existence-air, water, food. But "intrinsic value" cannot be measured in monetary terms. The intrinsic value of a bushel of wheat is due to the fact that it will support the life of an individual for a certain definite time, but this fact does not enable us to measure or to express that value in monetary terms. It has often been proposed to adopt as a measure of the value of any product the quantity of labor necessary to produce it, but this method is of limited application, and will not apply to what may be termed "intrinsic values." For many reasons it might be well, while assenting to the fact that any material may he intrinsically valuable, to abandon the use of the term " intrinsic value." One of these reasons is the tendency to confuse the idea of intrinsic value with a value that is conferred by economic conditions, that is purely artificial and that may be permanent or evanescent; Intrinsic value must from its nature be permanent and unchangeable.

Jan 7, 1913

By Warnie Flint

PERSONAL INJURY ACCIDENTS According to statistics compiled by the National Safety Council, US Bureau of Mines, American Medical Association, and other agencies, accidental injuries cause more deaths than all the leading diseases. NO one is immune to an accident. Probably the best way to describe an accident is to say that it is an unexpected happening. The automobile driver is not expecting a terrifying crash, the electrician does not expect to be electrocuted, nor is the coal miner expecting the roof to fall on him. All personal injuries will not result in death. There is a multitude of victims who arc living proof of what accidents can mean to an individual-victims who are blind, paralytic, missing arms, legs, etc. In most instances the earning power of these individuals is gone, and they arc utterly dependent upon family or welfare. For many years there seemed to be an attitude that prevailed in industrial America that accidents were inevitable, and that so many fatalities and injuries should be expected. This, of course, was utter nonsense. Since the birth of such organizations as The National Safety Council, American Society of Safety Engineers, and the US Bureau of Mines, much progress has been made in reducing accidents. The enactment of compensation laws greatly contributed to the progress that has been made. Does this mean that all accidents can be prevented? Unfortunately, it does not. Human psychology indicates that men will work unsafely or perform unsafe acts for the following reasons : 1) Lack of Knowledge or skill. 2) Conflicting motivations, such as: (a) to be more conformable, (b) to save time or effort, (c) to be accepted by a group. 3) Physical or mental condition. Nearly everyone desires his own safety, hut not all individuals are willing to do what they know to do to insure their own safety.

Jan 1, 1981

By Gerhard Derge

METALLURGISTS have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steelmaking of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxidizer in rimming steels.1 Likewise, the effectiveness of boron as an alloying agent has been demonstrated, 2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron, Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B203 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. EXPERIMENTAL PROCEDURE No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The most satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron 5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period of time. However, by using the rotating

Jan 1, 1946

By D. A. Dahlstrom

Although the liquid-solid cyclone is a relatively recent innovation in the field of coal preparation, various authors have already indicated three distinct applications to operations encountered in the modern tipple. Driessen's articles and work at the Dutch State Mines exhibited its possibilities in the bene-ficiation of fine coal with apparently high efficiencies down to the 200-mesh fraction. l,2,3,4 Other publications point out its use as a recoverer, thickener, and preliminary dewatering agent of fine coal which in too many cases is being wasted due largely to former high operating cost limitations.M Finally, certain authors have emphasized the practicability of applying the cyclone to the elimination of coarse and fine solids from water slurries in the tipple in order to produce a water suitable for recycle purposes containing only minute particles far below the 200-mesh size.6 This would result in a closed water system for many cases, with its accompanying economic and operating advantages to locations where water quantity and quality problems are severe; better operation of washing equipment using a consistent water devoid of injurious fine particles; lowered maintenance costs due to the lesser abrasion resulting when the fine abraiding particles are removed; and the greater ease of disposing of refuse streams of reduced volume containing greater percentages of solids. While the three applications have been indicated to be feasible, only a meager amount of data is available on capacities and solid elimination eficiency as a function of design variables and cyclone friction loss. This information is essential for the optimum use and construction of the solid-liquid cyclone, and accordingly, work on the problem was initiated at Northwestern University. For the unfamiliar reader, briefly the cyclone consists of a cylindrical section mounted above a truncated cone. The feed nozzle enters the cylindrical ring tangentially with the underflow nozzle permitting discharge of the concentrated solids located at the apex of the cone. The overflow nozzle through which the clarified water exits is centered in the cylindrical section at the top of the cyclone. Half sections of experimental cyclones will be found in Fig la and 6. The feed slurry enters with a tangential velocity, thus creating a spiral pattern of high centrifugal force. The solid particles of sufficient size and gravity are ejected outward to the walls and spirally discharge to the underflow. Most of the water with uneliminated fine solids moves radially inward along the path of the outer

Jan 1, 1950

By Benjamin Miller

FROM earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw lime-stone or products made from it. Anyone familiar with modern manufacturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date.

Jan 1, 1935

NEW MEMBER, The following list comprises the names of those persons who became members during the period Mar. 10 to Apr. 10, 1915: Members ADAMS, Louis WINFIELD, Supt., Rolling Mills, Lehigh Plant, Bethlehem Steel Co., So. Bethlehem, Pa.. ALLEN, ARTHUR WATTS, Mine Mgr Rodeo, San Juan, Argentina., BALL, EDWIN MARCOTTEL, Mine Supt., Ishkooda. Mines, Care Tenn. Coal, Iron & R. R. Co., H.F.D. 1, Birmingham, Ala. BOLN, CHARLES A., Oil salesman 135 S. 2d St., Philadelphia., Pa. BOYD, DAVID F., Naval Officer Navy Department, Washington, D. C. CAPERTON, GEORGE HENRY Charleston, W. Va. COGGESHALL, GEORGE W., Chem. Engr., Institute of Industrial Research, Washington D C

Jan 5, 1915

By J. H. Johnson, H. J. Schock

The cases of no auxiliary ventilation and ventilation with tubing were mathematically modeled, using a turbulent dispersion model. The Scooptram® used to load is modeled as a variable-speed, variable-strength source of pollutants moving in and out of the dead-ended drift. Model predictions are compared to experimental measurements. A parametric analysis was performed to determine If a relationship existed between C02 and NO levels. It was concluded from this analysis that when modeling a load-haul-dump cycle, it is necessary to use a model that can predict changes in source strength as well as source location. Carbon dioxide was used as a tracer to calibrate the model since, knowing the fuel flow rate, it is possible to calculate C02 production. The model was then verified after this calibration process using additional experimental results. With the calibrated model, it is possible to predict pollutant concentrations at any location in the heading using an engine map and the previously calculated flow field.

Jan 1, 1984

By Mahesh C. Jha

Arsenical gold ores occur in many parts of the world, including numerous mines in Canada and the western United States. Free gold is often finely disseminated in the grains of sulfide minerals, arsenopyrite, pyrite, orpiment and realgar. Generally a sulfide concentrate is produced by flotation. Arsenical ores or concentrates are not amenable to direct cyanidation and therefore are considered refractory. A wide variety of roasting equipment and conditions have been used by the mills to remove arsenic and sulfur from these concentrates. The resulting calcine is easy to cyanide and gold is recovered from the cyanide solution by zinc dust cementation. Room-temperature potential-pH diagrams and high-temperature phasestability diagrams are presented to discuss the chemistry of the gold cyanidation, cementation, and roasting steps in the presence of arsenic. The environmental aspects of arsenic discharge are also included.

Jan 1, 1984

By Joe L. Ratigan

INTRODUCTION Rock mechanics engineers are seldom concerned with obtaining the tensile or fracture strength of brittle rock at low mean stresses. The reason for this is two fold. Firstly, the behavior of many excavations in brittle rock is controlled by the inherent discontinuities in the rock mass. Because of the jointing and faulting, tensile strength is usually taken to be negligible. The second reason that tensile strength is seldom obtained in the laboratory is that the technology of utilizing this strength measure in design is undeveloped. Despite the fact that tensile strength of brittle rock is often ignored, there are a number of applications in rock mechanics wherein the knowledge of tensile strength is of fundamental importance. The apparent tensile strength must be known in a hydraulic fracture experiment if the state of in situ stress is to be determined from the initiation of the hydraulically induced fracture. In certain underground situations, the apparent tensile strength of intact rock beams defined by jointing or bedding planes is important in determining required rock bolting. Numerous other situations require a knowledge of apparent tensile strength including such high technology uses of underground space as geothermal energy extraction and LPG storage. Three observations are invariably made when intact rock samples are taken into the laboratory and tested to determine tensile strength. (1) The apparent tensile strength depends on the sample size (the 1 arger the specimen, the lower the tensile strength)

Jan 1, 1982

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By F. G. Miller, R. C. McFarlane, T. D. Mueller

During the process of gas storage in pressure-depleted oil reservoirs, it has been observed that in some instances additional liquid oil is recovered and that the composition of the storage gas is materially altered. A mathematical study was made of the dynamic behavior of such a depleted oil reservoir undergoing gas injection. The important variable considered in this study, not included in previously published work, was that of compositional effects on the phase behavior of two-phase flow. Pressure, saturation and component composition profiles were developed for a linear, horizontal and homogeneous porous medium containing oil and gas but undergoing dry gas injection. Special new techniques were developed to overcome the problems of numerical smoothing which arise in the solution of the equations representing such systems. The method of solution includes the development of partial differential equations describing the behavior of the system, representing these equations by finite difference approximations, making certain simplifying assumptions and, finally, applying methods of numerical analysis with the aid of a high-speed digital computer. In an example calculation, results using the mathematical model are compared with field observations made on a gas storage project in Clay County, Tex. This field project involved a depleted oil reservoir used 'for gas storage and gas cycling purposes. As a result of these processes, the reservoir yielded substantial amounts of secondary oil, both in the form of stock tank oil and as vaporized products in the produced gas. The methods derived in this study may be applied to a variety of oil reservoir problems which are dependent on compositional effects. In recent years the number of oil reservoirs being used for gas storage purposes has increased greatly, and there has been at least one published account of additional oil recovery resulting from gas cycling a depleted oil reservoir after repressur-ing with dry gas for storage purposes. Additional oil recovery from oil reservoirs resulting from gas storage operations could become an important secondary recovery process. This is especially true since the use of natural gas in large metropolitan areas continues to increase and more gas storage volume near these areas is needed. These facts provided the motivation for the work reported here. This paper reports on a study of the inter-relations of composition, saturation and pressure changes which occur when hydrocarbon gas is injected into an oil reservoir system. From an understanding of the process, prediction methods may be developed for use in forecasting the secondary recovery products from gas storage operations in oil reservoirs and, consequently, .the economics of such projects can be developed. The process of storing hydrocarbon gas in an oil reservoir and the cycling process both involve the transient multi-phase flow of oil reservoir fluids with changing fluid compositions. There is a scarcity of work published on the subject. One of the first laboratory models developed to study a problem similar to the one posed here was published in 1948 by Standing, Lindblad and Parsons. l They developed a model to study gas condensate recovery by gas cycling, including the effect of heterogeneous reservoir permeability. Their results showed the compositional effects of injecting a gas of known composition into a two-phase condensate reservoir of known composition. A major finding of their study indicated that maximum oil recoveries from gas cycling projects result when low cycling pressures are used. Previous to their work it was generally considered

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By J. L. Jorstad

The hypereutectic Al-Si alloys 390 and A390 have wear characteristics superior to any of the more common aluminum casting alloys. This excellent wear resistance, coupled with good mechanical properties, high hardness, and low coefficient of thermal expansion, has made these alloys candidates for the all-aluminum internal combustion engine, the application for which they were primarily developed. A390 alloy is intended for sand and permanent mold casting, and requires a lower iron ccxltent (0.5 pct maximum) than its die casting companion 390 alloy (0.6 to 1.1 pct Fe). The 17 pct nominal silicon in these alloys provides sufficient quantities of the hard primary silicon phase to assure a high degree of wear resistance, yet little enough of this phase, to minimize the casting and m achining problems associated in the past with the hypereutectic alloys. The mechanical and physical properties of 390 and A390 alloys are competitive with the best of the common aluminum casting alloys with the exception of low ductility. This low ductility is not considered a detriment, since in many applications these alloys replace cast iron. Corrosion resistance is similar to the standard alloys 380 and 333. Numerous parts, of varying degrees of complexity, have been cast of alloys 390 and A390, including engine blocks and heads. The deviations from normal good handling and casting practices that are required for the alloys are those associated with the presence of the primary silicon. To obtain optimum strength and machinability, the molten alloys should be treated with phosphorus to refine the primary silicon phase. Care must be exercised to properly control the pouring temperature and rate in order to minimize primary silicon growth and segregation. AUTOMOTIVE engineers have for years recognized the advantages of lighter weight and better heat transfer that aluminum could offer as material of construction for engine blocks. These advantages alone, however, are insufficient justification for acceptance of aluminum engines by the automotive industry. To be acceptable, an aluminum engine first must pass all tests to which cast-iron engines are subjected, and, in addition, must represent no cost penalty in manufacturing. None of the conventional aluminum casting alloys have sufficient wear resistance to withstand the tests to which cast iron is subjected as a cylinder bore material, and recent attempts to manufacture aluminum engines with cast-in-place iron sleeves could not compete costwise with the equivalent cast-iron engine. The prerequisite to an acceptable aluminum engine seemed to be a casting alloy with a high degree of wear resistance that would eliminate the necessity of cast-in iron sleeves or liners. The hypereutectic A1-Si alloys 390 and A390 have met this challenge.' Combined with modified pistons and a patented cylinder bore surface finish,2 the performance of these alloys in more than 1300 cold start and cold scuff tests, over 3500 hr of dynamometer wear and endurance tests, and more than 350,000 miles of road tests leaves no doubt as to the feasibility of running on bare aluminum cylinder bores. ALLOY DEVELOPMENT The desirable characteristics of the hypereutectic A1-Si alloys have been recognized for some time. Their excellent wear resistance and low coefficient of thermal expansions have been used to advantage in the production of diesel-type pistons in Europe and to a limited extent in this country. The major contributor to the good wear resistance of these alloys is the extremely hard primary silicon phase in the microstructure. Although the percent silicon used experimentally has been much higher, most commercial alloys have ranged from about 14 to 25 pct. Generally, as the silicon content is increased, wear resistance increases, and the coefficient of thermal expansion decreases. With increases in silicon, however, machinability and cast-ability tend to suffer. The development of a satisfactory aluminum engine block material at Reynolds involved the testing and evaluation of many alloys, covering a wide range of silicon contents and numerous variations of iron, copper, magnesium, manganese, and other alloying additions. Castability, mechanical and physical prop-

Jan 1, 1969

By H. L. Marcus, C. D. Turk

Titanium was physically vapor-deposited by electron beam high rate evaporation. Rates of 50,000 and 85,000Å per min at deposition temperatures of 480°, 535°, and 595°C were used. Deposited thickness ranged front 0.004 to 0.010 in. The evaporated titanium had a high degree of basal Plane texture. The specimens were tested in tension at temperatures ranging from 78° to 520°K. From the data, the yield stress, thermal component of the yield stress, and work hardening characteristics were found as a function of temperature, deposition rate, and deposition temperature. It was found that Taylor's equation, best fit the work hardening data with m = 1/2. MANY investigations have been made on the tensile deformation characteristics of commercial- and high-purity titanium.1"7 The data obtained from these experiments emphasize the fact that the mechanical properties are generally related to the method of production. The correlation of mechanical properties to production history arises from the dependence of impurity concentration on the extraction and melting technique used. Additional effects are derived from crystallographic texturing which can result from fabrication history. Lee and Backofen8 and other investigators9 have shown that crystallographic texturing in titanium sheet has a significant effect on the deformation characteristics. Bunshah and Juntz10 prepared high-purity titanium by high rate physical evaporation techniques. These authors found the deposited material to have a columnar structure with grain sizes ranging from 12 to 104 µ, depending upon the substrate temperature. The room-temperature strengths of the coarse-grained distillate were similar to arc-melted, rolled. and annealed crystal bar titanium. Commercial-purity titanium was also produced experimentally in our laboratory using high rate physical vapor deposition techniques. The commercially pure material has a finer structure than the high-purity distillate,10 and is highly textured. Since the method of preparation and degree of texturing affect the mechanical properties, a research program was initiated to determine the temperature dependence of the yield stress and work hardening characteristics as a function of high rate deposition parameters. This paper relates the results of the investigation. EXPERIMENTAL A) Material Preparation. The titanium was received in the form of commercial-grade 0.096-in.-diam wire which has a composition of 0.016 pct C, 0.0037 pct N, 0.110 pct 0, 0.011 pct H, 0.05 pct Mn, 0.051 pct Fe. balance Ti. The wire was continuously fed into a vacuum evaporation unit as shown schematically in Fig. 1. The deposition chamber was evacuated, purged with argon, and reevacuated to a pressure of 10-5 Torr which was maintained during deposition. A focused electron beam was used to evaporate the titanium from a water-cooled copper crucible. The titanium vapor was condensed onto a preheated titanium substrate. The temperature of the substrate was controlled within ±5°C for the deposition temperatures of 480°, 535°, and 595°C. Control of the input power enabled the use of two deposition rates. 50,000 and 85,000Å per min. The evaporated titanium had a final analysis similar to that of the input titanium, within experimental limits. B) Testing. The evaporated titanium was physically stripped from the titanium substrate and machined into tensile specimens with 1-in. gage lengths. In addition, tensile specimens of as received annealed 35-A titanium sheet with a 20 µ grain size and 45 pct cold-rolled 35-A were also prepared. All specimens were tested in tension in an Instron at a strain rate of 3.3 x 10"4 in. per in. per sec. Proportional limit has been used as a measure of yield strength. Tests were conducted at 78°, 220°, 300°, and 520°K. Metallography, X-ray diffraction, and electron microscopy were used to correlate structure with the deposition parameters and mechanical properties. Room-temperature X-ray measurements were made to determine the phases present. Pole figures and a scans were made to determine deposition texture. Because the vapor deposition was symmetrical about the normal to the substrate, there was no preferred di-

Jan 1, 1969