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By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By A. W. H. Morris, E. A. Steigerwald

The jatzgue beizazriov oj Mietal matrix co))zpos~tes in tension -lensiom loading has been imestigated as a junction of Dolume fraclion veinfovcelnent using the model systems of a silver matrix reinforced with contlnuous or dzscontztinuous aligned tungsten jilamenls and continuous aligned steel filamenls. Appreciable impvocetnents in fatigue strength were obseved in all syslems inzvesLigated, the degree of sl renglhenng-increasing with increasing volume fraclion of reinforcement. The mode of fatigue failure was found to be a function of colutrre jp-actiotz and was also noted to be controlled by the relative fatigue and strength characlerislics of the matrix and reinforcemenl. THE advantages to be gained by suitably incorporating high-strength filaments or whiskers into metallic matrices are well-recognized.' To date emphasis has been placed on the experimental determination of tensile strengths and elastic moduli of metal matrix composites measured parallel to unidirectionally aligned filaments. Several attempts have been made to relate experimentally measured tensile properties to theoretical values calculated from the properties of the components on the basis of the relatively simple "rule of mixtures" analysis. However, relatively few data have been reported in the literature on the fatigue behavior and mechanism of fatigue failure of metal matrix composites. In a study of fatigue crack propagation in aluminum plus steel wires and aluminum plus tungsten wires, Forsyth et a1.2 found that the incorporation of small numbers of filaments suitably dispersed were capable of substantially reducing the rate of fatigue crack propagation. For this purpose, the strength of the filaments appeared to be more important than the aspect ratio and the authors reported that parallel filaments were not the most favorable orientation for increased strength. In a basic study of the fiber reinforcement of metals, Williams and 0'brien3 report preliminary results which indicate a considerable improvement in fatigue strength in reversed bending fatigue of a steel wire-reinforced aluminum alloy composite. In a study of the influence of interfacial bonding on fatigue behavior, Baker4 has also reported improved fatigue properties in stainless steel-reinforced aluminum composites. In contrast, Ham and place5 report that, although tensile properties are improved greatly by filament reinforcement, the reinforcement of copper with continuous, brittle tungsten wires up to 23 vol pct was comparatively ineffective against fatigue. The authors attribute the poor fatigue properties of the composite to fatigue hardening of the matrix at the tips of cracks which can build up stress concentrations sufficiently large to fracture proximate filaments. Baker and cratchley6 failed to find marked improvements in the reversed-bending fatigue properties of silica-reinforced aluminum. The study was complicated by the complex behavior in a composite during the compres-sive half-cycles imposed in this type of loading. This was manifested in the failure of the composites by de-lamination, a contributing factor being the presence of aluminum oxide at the matrix-filament interface. Prior to the general acceptance of filament-rein-

Jan 1, 1968

By Frederic E. Carter

THERE have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

Jan 1, 1928

Gentlemen of the American Institute of Mining Engineers.—As you well know an application is about to be made to Congress, by the American Society of Civil Engineers, for the appointment of a cornmission composed of persons skilled in the production and use of iron, steel, and other structural materials, whose duty it shall be to test the strength, elasticity, and other quatities of such materials ; not simply the substances used as such, but the members of large structures composed of such materials, of the forms and sizes in which they are actually used. As I understand, the papers that will be read here to-night will have for their object to show the necessity for such tests, and therefore the necessity for the commission asked for. As the representative of the Society of Civil Engineers, I have to thank you, gentlemen of the Mining Engineers, for the great zeal with which yon have taken up this subject, and seconded the efforts of the Civil Engineers; or, perhaps I ought rather to say, initiated the efforts to get a suitable commission appointed to obtain most vitally important information which it is admitted on all hands we do not now possess. In drawing up the memorial to Congress, in connection with some of the ablest and best informed of our Society, and in all the discossions on the subject, I have been struck with the emphasis with which the confession is made, that so little is known of the strength of the larger-sized members constantly used in building structures of the magnitude which the present requirements of the country now demand. I presume the remarks made to-night will bring this out very prominently. This is no disgrace, for with the means here-

Jan 1, 1882

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By H. F. Silliman, Daniel R. Hull, John R. Freeman

IN the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of coldwork and a considerable number of anneals. This condition has been disturbed by the prep0nderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2: 1 brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. HOT-ROLLED 2:I BRASS For illustration, therefore, a typical cake of hot-rolled 2: 1 brass has been chosen. This was rolled to a slab 7/8 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. 1. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it w0uld be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

Jan 1, 1951

By S. B. Christy

The practice of the cyanide-process of gold-extraction has brought to light many important contradictions of familiar chemical analogies, which still obscure both the theory and the practice of the art with distinctions subtler and more difficult to make or follow than those which delighted the heart of the old-time metaphysician. Yet Nature herself has drawn these distinctions; and if we hope to succeed in this modern search for the Golden Fleece, we must be able to follow her through the winding labyrinth. There are so many phases of this question that I shall attempt to touch on only one of them at this time, but it is one that lies at the root of many others. In reviewing my paper on " The Solution and Precipitation of Cyanide of Gold,"* Mr. E. B. Wilson contends† that" in the solution of gold by means of alkaline cyanides the various reactions are determined, as to their order and intensity, by the relative position of the elements concerned in the electro-chemical series, or series of voltaic tension." In a modified form this statement is probably true. That is to say, the difference of electrical potential in any closed electrical circuit determines the nature of the reactions which ensue. But the matter is not so simple as Mr. Wilson assumes. Recent investigations show that the order of the metals in the electro-chemical series depends not only on the nature of the elements themselves, but also on the chemical composition of the solution in which they are placed; its degree of concentration; its temperature; and, in the case of gases, on the pressure. Unless all these conditions are taken into account, inferences drawn from the electro-chemical series are likely to prove more

Jan 1, 1901

By P. A. C. Wilson

Instantaneous outbursts of carbon dioxide in coal mines have occurred in Germany only in one part of the Waldenburg-Neurode mining district.' This mining region comprises the northeastern fold of the "Innersudetian" coal basin. The basin (Fig. 1) is in the form of a geologic trough approximately 60 km. (37 miles) long and 30 to 35 km. (19 to 22 miles) broad and is enclosed on three sides by ancient truncated mountain ranges—the Riesengebirge, the Bober-Katzbachgebirge and the Eulenge-birge. Only the southeastern part of the trough is not enclosed by mountains of older rock formation. The floor of the basin before the building up of the coal measures was formed on the western, northwestern and northeastern borders by the material from Archean rocks (gneiss and mica schists); in the northern part over this was deposited the Silurian formation. The carboniferous period is represented both by the Lower ("kulm") and Upper Carboniferous, with an unconformity between the stages; that is, the kulm was tilted up and partly eroded before the Upper Carboniferous was deposited. The kulm is a salt-water formation (with marine fauna) but Upper Carboniferous rocks are nonsaline water deposits, with fresh-water flora only. The Lower Silesian coal measures were thus formed in a lime basin fed by the running water coming down from the mountains. As already indicated, the bottom series of the Upper Carboniferous formation, termed "Waldenburg strata" were laid down unconformably on the Lower Carboniferous. Over the Waldenburg strata there are the "Weisstein strata," an intermediate barren stage without coal beds, 400 to 500 m. (1300 to 1600 ft.) thick. Another unconformity followed, which is overlain by the '(Saarbrucken" series, which contain the upper coal measures, and the ('Ottweil" strata. In the last named, it is only on the southwestern fold that beds of coal are developed.

Jan 1, 1931

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

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

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

Jan 1, 1949

By Russell Dayton

THE metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concern-ing the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chal-cography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Konigsberger,(1)? in 1909, was the first to apply polarized light to the microscopic study of

Jan 1, 1935

[NORTH AMERICA UNITED STATES Alabama BIRMINGHAM BURROWS, WILLIAM C. CORD, RICHARD H. COSTON, OTIS D. JR. FAIRHOPE RUFFLES, WILLIAM R. HUNTSVILLE WAGGONER, JERRY B. MOBILE PETROUTSON, PETER C. SELMA JONES, JAMES J. JR. UNIVERSITY CUDWORTH, JAMES R. JONES, WALTER B. RICHARDS, EDWARD F.]

Jan 1, 1961

By F. H. Wilson, R. M. Brick

WITH the papers of Palmer and Smith1 and of Burghoff and Bohlen,2 published in 1942, understanding of the problem of the development of ears on deep-drawn brass cups was brought to the point where, from a practical standpoint, producers of brass sheet could keep earing under control. However, these very practical results raised questions concerning the reasons for the observed behavior. Since plastic deformation is fundamentally a function of crystallographic slip, these reasons must be considered in the light of the textures to be found in the annealed sheet. Various attempts have been made to interpret the mechanism of ear formation by correlation with the preferred orientation and the anisotropy of the sheet. However, none of these has satisfactorily explained why ears are usually found in the rolling and transverse directions for copper but at 45° to these directions for brass. This paper offers additional data on these two related subjects and has been divided into two sections. The first section provides a survey of the recrystallization textures of brass as affected by annealing temperatures and prior reductions, and an account of the earing behavior which accompanies these textures. The second section reports new data on the anisotropy that accompanies a characteristic texture for brass and endeavors with partial success to establish the factors that account for the difference in earing behavior between copper and brass. EARING BEHAVIOR OF BRASS Review of Textures The recrystallization texture of severely rolled brass was first reported by Bass and Glocker.3 The preferred orientation to which this texture, obtained from metal annealed at 500°C., was most akin was (113)[112]. This texture has been confirmed by Bauer, von Göler and Sachs;4 Brick;* Brick, Martin and Angier;6 and Cook and Richards7 who, in general, used annealing temperatures under 500°C. Bass and Glocker3 also reported the recrystallization texture at 850°C. to be the same as at 500°C. They analyzed their textures by means of single photograms obtained with white radiation. The photograms for both temperatures are reproduced in their paper, and there is a strong similarity between the two. However, for the latter temperature, the number of spots registered on the film was remarkably large for the grain size to be expected, and the authors made no mention of using a technique that would integrate a large enough area of the specimen to produce so many spots. The only other attempt to determine textures resulting from high temperature

Jan 1, 1945

By H. S. George

On one occasion when it seemed desirable to reveal under the microscope not only the metallic structure of an alloy, but certain small non-metallic inclusions that are ordinarily obliterated by etching, it was discovered that, by partly eclipsing the illuminating pencil of light rays, the residual light was thrown on the object from one side and the structure was brought out in relief. At the same time, the non-metallic inclusions were retained in clear view. In this first demonstration of lighting obliquely through the objective a card was thrust part way into the light beam between the arc iris and the light filter; the shadow of the card on the filter served to locate its position. Next several stiff-paper disks of various diameters were mounted on flexible wires; some plasticine on the other end of the wires made it easy to adjust and maintain a disk at any desired position in the light beam. To facilitate manipulation, an assortment of disks was mounted on a wheel, as shown in Fig. 1. The purpose of partly eclipsing the light beam was discussed in an earlier paper.' There it was pointed out that the usual methods of illuminating opaque objects for microscopic examination lend an unnatural appearance to the view, while the new method, which has been termed conical illumination, revels the true relationship of constituents by simulating natural lighting. In nature, all objects are lighted diffusely, or by light predominating from one direction, or by a combination of diffuse and directed light. Under these conditions, objects appear to have three dimensions—they possess relief. The kind of illumination known to metallographists as vertical or axial results in an unnatural appearance, as a large proportion of the illuminating rays are parallel to the line connecting the eye with the object, a condition almost never met in nature. Microconstituents

Jan 1, 1924

By T. H. Oxnam

The predominating value of the ores now being treated by the Palmarejo and Mexican Gold Fields, Ltd., is silver, although some gold also is carried. The present method of treatment consists of wet-crushing and concentrating, followed by the cyanidation of the un-roasted sands and slimes. The sands are treated by leaching, and the so-called " accumulated slimes " by a system of agitation and decantation. It is only within very recent years that the cyanidation of unroasted silver-ores has been commercially successful. In fact, at the time operations were begun at the cyanide-plant at Chinipas, February, 1902, I knew of no other leaching-plant treating similar ores successfully. The cyanide treatment of the Palmarejo ores differs but little from the ordinary practice in cyaniding gold-ores; and perhaps but little, if any, new information concerning the metallurgy of silver is to be gleaned from it. Palmarejo Mines. The Palmarejo mines are located in the southwestern part of the State of Chihuahua, Mexico, on the foothills of the Sierra Madre mountains, at an elevation of 3,200 feet. The mills, 12 miles distant, are situated on the Chinipas river, near the town of Chinipas, which is about 150 miles northeast of Agiabampo, on the Gulf of California. Supplies are shipped via this port as this route is the best and most direct to the property. The ore-bodies in the Palmarejo mines have been deposited along a series of rock-fractures, caused by an intrusion of eruptive rock. The most important of these fractures or fissures, both in width and value, are the Prieta and Blanca veins, which

Jan 1, 1906

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman' and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964