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By W. F. Flanagan, D. H. Polonis, S. D. Dahlgren

Rotation diffraction patterns of Cu-4.84 wt pct Si polymystalline samples were taken during the course of isothel-ma1 affing of the suPersaturated a phase, a diffraction spots were obserzled to streak during the initial stages of aging, and this streaking was similar to the streaking of a spots observed earlier by Barvett with deformed super saturated samples of the same composition. Although it was suggested that stacking faults were the sole cause of styeaking in the deformed samples, the present study has shown that plates with one small crystallite dimension can also contribute to the streaking when there is lattice coherency across close-packed planes. THE decomposition of the supersaturated a phase in Cu-Si alloys has been reported to occur by means of both thermal and stress activation.1-4 According to the Cu-Si phase diagram,3 Fig. 1, the supersaturated a phase (fcc) is expected to transform during aging by the precipitation of the y phase. The results of earlier studies2,4 have indicated that metastable k phase (hcp with nearly ideal close packing) forms initially at temperatures below the eutectoid temperature, after which the k transforms to the a and y phases. Hof-mann et al.4 have proposed a metastable version of the phase diagram, showing the approximate boundaries for k formation below the eutectoid temperature. In view of the close-packed nature of both the a and k phases, it is essential to consider the role assumed by stacking faults in the transformation. Streaking effects have been reported by Barrett 1 in the rotating crystal X-ray patterns of strained Cu-Si alloys and were attributed to stacking faults rather than particle size effects. This deduction was based on the observation that streaks in the diffraction patterns did not occur tangent to the 220fee Debye ring. It is known that the atom movements involved in faulting leave some X-ray reflections unaffected while others are broadened,' and, in particular, it has been shown that faulting will not cause streaking of 220fee reflections tangent to the 220fee Debye ring as would be expected if all the reflections were broadened.' The formation

Jan 1, 1967

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By Arthur T. Ward

DESPITE the intense preoccupation of most of those members connected with the mining, concentration, and reduction of iron ores, the luncheon and subsequent technical session of the Eastern Magnetite Committee were exceedingly well attended. Many of the older faces were absent, but new ones took their places. More than sixty, all told, took in the technical session. Chairman Crockett opened the session by calling upon Meredith E. Johnson, whose paper, with its accompanying graph, was in reality a comprehensive historical review of iron mining from colonial days to the end of 1941. with some notes on current expansion which indicates that New Jersey is destined to become a still more important. factor in the production of magnetite ores.

Jan 1, 1942

By Jerry Tien

Mine regulators are normally used for proper air distribution in underground mines. They are deliberately introduced resistance in the regulated airway, and by altering sizes, they can distribute specific air quantities to regulated splits and free splits (4, 5). The enactment of the Federal Coal Mine Health and Safety Act of 1969, the Federal Mine Safety and Health Amendments Act of 1977, and the regulations adopted by the Mining Enforcement and Safety Administration (now called the Mining Safety and Health ministration) prompted greater discussions of optimal mine regulator locations because of the Act's stringent ventilation requirements (2, 3). For example, by requiring the separation of the air used in the belt haulage entries from the intake and return airways, the regulations required the creation of a third type of airway---the neutral airway, as opposed to the intake and return airways, adding to the complexity of a mine's ventilation network. It is the intent of this report to show that panel regulators should be located in intake airways at the neck of a panel for a blowing fan system and in return airways at the neck of a panel for an exhausting fan system in order to achieve optimal air control. A computer simulation model is used to determine optimal mine regulator location.

Jan 1, 1983

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By R. O. Day, R. S. Dean

In constructing a theory of the flow and hardening of metals, v necessarily make use of such phenomena as seem to be universal1 observed in metals. It is, therefore, a matter of concern to the con structors of such mnemonic systems if one or two of the group classific as metals show anomalous behavior. Such egregious phenomena observed in pure or nearly pure iron in the reaction of its mechanic properties to low-temperature annealing after cold work and to increase temperature of testing. In short it has been generally observcd tha iron, as an outstanding exception among metals, increases its hardnes and strength by low-temperature annealing after cold work,' and alt by increase of testing temperature to the range of 150" to 300" C. The investigation here recorded was made then with the object ( ascertaining if similar phenomena were observed in high-purity iro and, if not, to the presence of which impurities these phenomena coul be traced. Experimental Procedure Three kinds of iron were taken for a study of hardening by rehcatin after cold work: 1. Vacuum-melted electrolytic iron; melted in an Arsem furnace in a magnesia crucible. That this iron was of high purity is indicated b a magnetic permeability above 20,000. 2. Electrolytic iron melted in air in a small laboratory furnace. 3. Armco iron, commercial material. These materials in the form of forged bars, annealed at 980" C. in vacuum, were reduced 30 per cent. in thickness by cold rolling and the reheated to temperatures varying from 100' to 500' C. The Rockwe hardness number was measured after each treatment. The results and shown in Fig. 1, curves 1, 2 and 3.

Jan 1, 1929

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966

By L. Webster Wickes

The bad effects of arsenic in commercial copper are well-known to metallurgists. The refining of copper by electrolysis eliminates practically all of the arsenic, provided certain requirements are fulfilled. The first, and most important, of these requirements is, that the voltage of the depositing current shall not be too high. It has been known for some time that the percentage of arsenic in the deposited copper increases with the voltage. To investigate the relation between the electro-motive force (e.m.f.) and the freedom of the precipitated copper from arsenic, the experiments were made, of which a brief summary is here given: I made three copper-arsenic alloys, containing respectively 3.56, 2.24 and 0.96 per cent. of arsenic. From these alloys I cast several anodes. For cathodes I used sheets of thin copper,

Jan 1, 1905

ABIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has three major awards to make annually and one special prize for excellence in technical papers, as follows. The Robert W. Hunt Medal and Prize, The J. E. Johnson, Jr., Award, the James Douglas Medal, and The Lewisohn Platinum Prize to senior members. ROBERT W. HUNT MEDAL AND PRIZE The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting' ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules ? 1 The award shall consist of two prizes, first of a gold medal, second of a sum of money, a certificate to accompany each prize. The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2 The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel The scope of the term "iron and steel" shall be determined by the sub-committee considering the awards In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material

Jan 1, 1923

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Eugene N. Cameron

Pegmatites of these areas have become important sources of beryl and lepidolite and have yielded cassiterite, columbite-tantalite, and other minerals. Examination of about 60 of these pegmatites leads the author to question the opinion of earlier investigators that the concentrations of beryl, lepidolite, and columbite-tantalite found have mostly formed by hydrothermal or pneumatolytic replacement of previously formed quartz-feldspar pegmatites. The author concludes, on the contrary, that present knowledge of the occurrence of minerals in zoned pegmatites can be applied to prospecting and mining of pegmatite deposits in these two areas of South West Africa. PEGMATITES occur in abundance in certain areas of South West Africa and in adjacent parts of northern Cape Province in the Union of South Africa. Some of the pegmatite deposits were prospected before World War I, and intermittent mining was done during the period between the two World Wars. The deposits of the Jooste lithium mines became an important source of lepidolite, and beryl, columbite-tantalite, wolframite, and other minerals were produced. Since World War II prospecting and mining have been carried on vigorously, with the result that South West Africa produced nearly 3000 tons of beryl during 1949 through 1953, together with more than 40,000 tons of lithium minerals, chiefly lepidolite and petalite. Small amounts of tantalite, columbite, and other minerals have also been produced during the postwar period. Most of this mineral production has come from two pegmatite areas roughly outlined in Fig. 1. One is the Karibib-Omaruru area of north central South West Africa. The second is the northeastern part of the Orange River pegmatite area, which extends into adjacent parts of Namaqualand, in northern Cape Province of the Union of South Africa. The writer visited the two pegmatite areas in July 1951. The visit was brief. but it gave an opportunity to compare some of the' pegmatites of these areas with those studied and described in detail by many investigators in the U. S., Brazil, and Canada during and since World War 11.'-l' The writer has attempted to determine, in a preliminary way, whether the concepts of internal structure and distribution of minerals in pegmatite bodies developed out of these studies are applicable to prospecting and exploration of pegmatites in South West Africa. Previous Work In an important series of papers (1929 to 1942) T. W. Gevers, H. I?. Frommurze, S. H. Haughton, G. K. Joubert, and other geologists of the Geological Survey of South Africa described and discussed the pegmatites of the two areas.*-" These works are the principal sources of information on the pegmatite mineral deposits of South West Africa. The investigations showed that in the two areas pegmatites are profusely distributed in pre-Cambrian rocks. These rocks are meta-igneous and metasedimentary units that have been folded and subsequently invaded by younger pre-Cambrian granites and by other igneous rocks. The pegmatites are considered to be genetically related to the pre-Cambrian granites. Pegmatites occur in the granite bodies themselves but are most abundant in the surrounding metamor-phic rocks, a pattern repeated in many pegmatite districts of the world. The origin of the pegmatites and the factors controlling the occurrence of mineral deposits in them were discussed at length by Gevers and Frommurze (1929)" and later by Gevers 14, 15 pp. 41-51, Ref.

Jan 1, 1956

By E. L. Dougherty, J. W. Sheldon

A numerical method for computing the dynamical behavior of fluid- fluid interfaces is described. Results of studies made to assess the accuracy and economy of the method on a computer are reported. It is concluded that it is practical to obtain digital computer solutions for fluid- fluid interface problems with two space dimensions. PROBLEM DEFINITION We consider two-dimensional flow in a rectangle as shown in Fig. 1, where a fluid-fluid interface divides the rectangle into two regions. The pressure is specified along the lower boundary (the injection boundary) and upper boundary (the withdrawal boundary). There is to be no flow of fluid across the side boundaries, which are walls of symmetry for the flow, and px = 0 along these boundaries. The fluids are incompressible, the absolute permeability and porosity is constant, and each fluid has its own constant mobility. Thus, the pressure satisfies Laplace's equation in each region. Across the interface, pressure is continuous and the normal component of fluid flux is 1. These conditions are shown in Fig. 1. The velocity of a point on the interface in the direction of the normal from Fluid 1 into Fluid 2 is U,/ Q, where Un is the normal component of volumetric flux at the point on the interface, i.e., For brevity, we call the problem defined above "Problem A". Problem A is a simple example of a dynamical fluid-fluid interface problem. However, the same numerical methods which we use to solve Problem A can be extended to the solution of a large number of fluid-fluid interface problems which are mathematical models for various oil recovery processes,l hence our interest in Problem A. We define the interface by prescribing the x, y coordinates of a finite set of points. These points are called "interface mesh points" and are illustrated by triangles or asterisks in the figures. Fig. 2 is a procedural (flow) chart displaying the main steps in the solution. We comment briefly on some of these steps in this section and then give further details in subsequent sections. For mobility ratio greater than one it is well known that Problem A is unstable.*2 Small amplitude,

Jan 1, 1965

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By N. J. Sather

A detailed description is given of Bunker Hill's concentration process employed at the company's lead-zinc property in the Coeur d'Alene district, Idaho. The plant is equipped to process 3000 tpd of Pb-Zn ore. The history of the Bunker Hill mine dates back to Aug. 26, 1885, when Noah S. Kellogg found the outcrop of the Bunker Hill orebody on the hillside of Milo Gulch above the present town of Wardner, Idaho. A small concentrator was erected in 1886, and before the railroad came, the mine output was transported by mule teams to the head of navigation on Coeur d'Alene Lake. After ten years of production, an interest was purchased in the Tacoma smelter at Tacoma, Wash., to which the entire output was shipped. In 1916 and 1917, a modern lead smelting plant and refinery was erected, and a modern electrolytic zinc reduction plant was built in 1927-1928 by the Sullivan Mining Co. which was 50 pct owned (and now totally owned) by the Bunker Hill Co. The first concentrator, a 100-tpd capacity plant, was built in 1886 near the Reed Tunnel in Wardner. The treatment consisted simply of crushing ore to 2 in. and then to 1/2 in. through rolls in closed circuit with a bucket elevator and trommel screen. The undersize was further sized in trommels to 10 mm and 3 mm. Oversize from the latter was treated in Hartz jigs. The 3 mm undersize was classified in crude hydraulic classifiers furnishing sands to sand jigs, the overflow being dewatered in a long V tank which supplied sands to a Cornish buddle and to Frue vanners. The concentrates were of excellent grade, old records showing assays of 69 pct lead and 29 oz. of silver per ton. Tailings were high inasmuch as the provision for treating the slimes was inadequate. Since the erection of the first mill, the Bunker Hill plant has gone through many changes and improvements. In succeeding years, the flowsheet was enlarged somewhat with Huntington and Chilean mills, vanners, tables, ball mills, and flotation cells being progressively added. In the transition period to the present day practice, the object was not only to improve the equipment for better mechanical performance, but to add new equipment whenever practicable so as to improve both grade and recovery of the product at a lower cost. For the modern plant and flow-sheet, see Figs. 1 and 2. The history of flotation at Bunker Hill dates back to 1913 when experimental work was done in a cell in which the pulp was circulated through a centrifugal pump set outside the cell and discharged against a baffle in the cell. The cell was built with a spitzkasten, and the quiet zone in the latter tended to let the froth break down before it got to the overflow weir. To remedy this situation, a belt drag with light metal flights was arranged for drawing off the froth over a ramp in each cell. Recovery of lead was not as high as present day practice, but was so much better than the vanners that the cells were multiplied gradually to eight cell units. The mill men called them mud hens. Flow between the cells was controlled by a weir, which determined the pulp level in each cell. These early machines were called Bunker Hill machines. The tailings were later treated in pneumatic scavenger flotation machines in a series, producing concentrates for retreatment in the Bunker Hill cleaners as well as the final tailings. This system of flotation served with minor changes until the Fahrenwald machine was developed at Bunker Hill during the period from 1921 to 1925. In 1925, the Fahrenwald flotation machine gradually replaced the Bunker Hill machine, although the Hearing pneumatic scavengers for retreatment of the tailings from the Fahrenwald machines were retained in the lead section until 1928. The use of the Hearing pneumatic machine for cleaning the rougher concentrates was begun in 1924. In 1941, plans were made for remodeling and modernizing the concentrator, the goal being a modern concentrator employing the latest equipment and milling practices. The old wooden building was to be replaced by a steel and concrete structure. Shortly after preliminary work got under way, the United States entered World War II and the demands for metals increased. To meet this requirement, the management decided to increase the capacity of the concentrator to 1800 tpd. This was accomplished in record time by the construction and operation of a sink-float plant. Installation of this plant was the first step in the general plan for modernization. In 1947 the concentrator (including the sink-float plant) was enlarged to handle 3000 tpd. Milling operations today are at the rate of 2300 tpd, five days per week. During 1959, 453,000 tons of ore was beneficiated. The Bunker Hill concentrator is in three sections: the crushing plant, a 3000-ton capacity storage bin, and the concentrator building. The crushing plant is of wood design with a gunnite coating on the exterior.

Jan 1, 1961

By C. P. Walker

Determining the distance to remote objects by observing the time required for sound to traverse the intervening space is an old practice. Attempts have been made to use this method for determining the fluid level in oil wells but as far as the writer is aware it was not found to be practicable, because vibrations in gas in the audible frequency range do not travel as well and as far as low-frequency pressure waves, which are capable of transmitting a greater amount of energy than can be transmitted by audible waves. Wood, in his book "Sound," states that in a given medium the range of sound transmission will vary inversely as the square of the frequency. The fact that the sound from a whistle having a low tone has a much lower attenuation rate than that from a whistle of high pitch is well known. Also, the pressure waves caused by cannon fire often rattle windows at points so distant that no sound of the cannon is heard. In 1932 P. E. Lehr and H. T. Wyatt, of the Shell Oil Co., experimented with the principle of the concussion, or pressure-wave echo, method of determining fluid levels in oil wells. They released compressed gas into the top of the casing, thereby creating a pressure wave, which traveled down the well and back again. Their experiments proved conclusively that, with the proper apparatus for recording the echoes and determining the velocities at which the waves travel, the method could be used successfully for determining fluid levels in oil wells. Wells are often equipped with from one to three tubing catchers and these together with the top of the liner are frequently above the fluid. Each of these obstructions reflects a part of the pressure wave. In such wells there may be, therefore, as many as five pressure-wave reflections. Thus it is obvious that in order to identify the various reflections and to determine therefrom the fluid level in a well it is necessary to obtain a graphic record of these reflections.

Jan 1, 1937

By H. R. Shidel

This paper summarizes the results obtained from the preliminary cementing of wells in an effort to cut off the bottom water. The object of this work was two-fold: (1) To prevent the oil sand from becoming flooded. (2) To plug off bottom water, thereby preserving the individual well and reclaiming production. Valuable suggestions and help have been given by the following named: Messrs. Kyle and La Velle, of the U. 8. Bureau of Mines; Magnolia Petroleum -Co.; Freed Oil and Gas Co. The cementing work was carried out under the personal supervision of L. J. Snyder. In an unpublished paper on the "Water Problem in the Augusta Field," 5. K. Clark reaches the following conclusions: (1) That the great amount of water present is bottom water, occurring in the Varner sand, the main producing or the 2500-ft. horizon, (2) That the only striking connection between structure and water is in .the area of the marked fault on the Ralston, E. C. Varner, and F. Varner leases in sections 8, 9, 16 and 17. (3) That the oil occurs in porous streaks, generally separated by finegrained, well cemented sand, which is barren. Possibly two or three such pay streaks may be found. That under a pay, fine-grained sand occurs, which is presumably barren at the time of drilling, but soon reveals water. The writer takes partial exception to the last point, because well defined shale, slate, lime, or hard sand breaks have been encountered in a great many cases, separating the pay streaks under which water is often found. This is not an invariable occurrence, as cases have been noted when the oil has been followed immediately by water in the same stratum. In an effort to overcome the water menace, the following methods of plugging were tried: (1) Plugging with wood, lead, and limit plugs. (2) Plugging with sand pumpings.

Jan 1, 1920

By Dale S. Preece

INTRODUCTION In 1975 Congress passed the Energy Conservation Act to establish a U. S. Strategic Petroleum Reserve (SPR) with a capacity of 750 million barrels of crude oil. The most economic storage medium was determined to be salt caverns leached in salt domes in Louisiana and Texas. Salt caverns existed at several sites when the reserve was created. These were obtained by the U. S. Department of Energy (DOE) and used to initiate SPR oil storage. In order to meet the storage capacity approved by Congress, new caverns also had to be leached. To support the resulting design effort, finite element computer programs have been used to determine the creep closure and structural stability of salt caverns Using site specific material properties including creep models, elastic moduli and fracture data, the finite element analyses have replaced earlier empirical approaches to cavern design. This report presents results of such finite element analyses to determine the best cavern roof shape and the minimum pillar to diameter ratio, P/D. These numerical predictions indicate that the current cavern design is safe. FINITE ELEMENT AND MATERIAL MODELING The finite element program used in this study has existed for approximately four years. Its theoritical basis (Key, et al, 1980) and application are well documented It was originally developed to predict the creep around mined openings In bedded rock salt for the Waste Isolation Pilot Plant (WIPP) The program was tested by modeling the creep of salt around a drift and by comparing the results with the predictions of eight other structural computer codes (Morgan, et al, 1981) Since then the program has had continual use for calculations to support the WIPP (Miller, et al, 1982) For about two years the

Jan 1, 1984

By Carl Henrich

Jan 1, 1893