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By Walter Rose

Theoretical expressions are presented to describe wetting and non-wetting phase relative premeability relations. These expressions have then been compared with existing published data, the conformance noted being sufficiently good to satisfy the requirements of some engineering use. As a consequence, it may be supposed that relative permeability characteristics of porous media now can be inferred from basic core analysis data, in a manner more convenient (although less direct) than presently available methods of experimental evaluation. INTRODUCTION This paper presents a new approach to the problem of relative permeability evaluation. A classification of published discussions of relative permeability concepts which have appeared in the petroleum literature will show that previously emphasis has been placed on methods of experimental measurement, on the interpretation of the data so obtained with respect to the variable properties of the system, and on theoretical and practical considerations which relate relative permeability to gross fluid behavior in petroleum reservoirs. Essentially, no detailed examination has appeared which treats the fundamental factors controlling the quantitative features of the relative permeability relation*, although cer- tain references can be Cited where a qualitative awareness of their existence and nature is indicated. This condition is explainable in terms of the recognized complexity of the problem, and in order to provide some basis for theoretical development, the general emphasis has been placed in the past on experimental procedures of evaluation, the validity of which, in principle, could be confirmed by the analysis of well and reservoir performance. However, because of the experimental difficulties which have been encountered (notably, difficulties due to the so-called "end effects"), and because of the general unreliability of field performance tests required to study the applicability of the data, relative permeability phenomena continue to be incompletely understood and described.? In this paper is examined the possibility of predicting relative permeabilities entirely from fundamental considerations. In addition, attention is called to certain important factors, previously unemphasized in the published literature, which now can serve as a basis for the eventual experimental confirmation of this and similar theoretical approaches, as well as the experimental solution of the problem in general. Therefore, the analysis presented herein has the dual purpose both of orienting future experimental activity and also of providing an immediate solution for the relative permeability porblem, sufficiently adequate for some engineering use. It will be seen that the conclusions reached are supported by theoretical and intuitive considerations, and they are not contradicted insofar as gross features are concerned by existing concepts and interpretations of published experimental data, except as specifically noted. Darcy's law, expressed simply as: k dp q = k/u dp/dx .......(1) where q is linear rate of flow (assumed horizontal), k is the † The poor comparison usually obtained between laboratory and field gas-oil ratios (c.f.. Fig. 4 of paper by L. E. Elkins) is illustrative of conditions which dimcourage unqualified acceptance of the results of previous studies except as presently useful approximations. In this connection, Evinger and Muskat have discussed in detail the discrepancy observed between field well productivity values and values obtained from the analysis of laboratory flow data.

Jan 1, 1949

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

Coal - Surface Mining Coal Preparation Coal Utilization Research and Development Health and Safety

Jan 3, 1976

By Robert D. Thomson

LISTED among strategic and critical minerals for stockpiling, mica is an important raw material in electronic and electrical equipment industries. Each year large quantities are consumed in the manufacture of television and radio tubes, radar sets, generators, transformers, electric toasters, and irons. Crude mica, which comes from the mine in crystals or in rough books of various shapes and sizes, is known as run-of-mine or book mica. Structural imperfections, impurities, rough edges, and defective laminae are removed by cobbing, rifting, and trimming to produce a marketable block mica or film mica.' After the rough books have been hand-cobbed to remove adhering rock, dirt, and crushed or defective mica they are rifted, or split. In the U.S. a straight-bladed knife is generally used for rifting. Products of this operation are classed broadly as untrimmed sheet mica and scrap. Sheet mica is any relatively flat piece sufficiently free from physical defects to be cut or stamped into specified shapes for industrial use. Sheet mica is classed as block, film, and splittings. Block mica is not less than 0.007 in. thick with a minimum usable area of 1 sq in. Film mica is split from the better qualities of block mica to groups of specified thickness ranging from 0.0012 to 0.004 in. Splittings are sheets with maximum thickness of 0.0012 in. and minimum usable area of 3/4 sq in. As virtually no mica splittings are produced in the U.S., they will not be discussed in this report. Small, low quality block is subdivided as punch and washer. Punch mica is thumb-trimmed material large enough to yield a circular disk of at least 11/2 in. diam for stained quality mica and 1 1/4 to 2 in. for clear quality. Poorer lots, often referred to as washer mica, are also included in the general term punch mica. Trimming, the next step in processing sheet mica, removes broken and ragged edges, loose scales, and other major imperfections. Trimming may be done with a knife, sickle, shears, or fingers. In the U.S. it is usually done with a 3-in. linoleum knife to obtain a bevel-edged cut. If ragged edges are broken off with the thumb and fingers, the mica is called thumb-trimmed. Full-trimmed is rifted mica trimmed on all sides with all cracks, reeves, and

Jan 1, 1957

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By ROBERT R. ABUOTT

(Cleveland Meeting, October, 1912.) THE practice of carbonizing steel for the purpose of case-hardening has assumed great commercial importance within the past, 10 years. Formerly, case-hardened steel was held in more or less contempt, since it. was considered a cheap substitute for tool-steel. This is no longer the case. The development of the motor-car industry, and coincidentally that of modern alloy-steels, has resulted in overcoming many difficulties formerly experienced in case-hardening. This result has been accomplished by increased knowledge regarding the analysis of the steel which would respond most readily to case-hardening, and by more careful methods of treatment of the carbonized steel. The ordinary method of carbonizing consists in packing the steel with the carbonizing-material in cast-iron boxes and placing them in a furnace at a temperature of from 1,500° to 1,900° F. for a time sufficient to give the required depth of cc case." The steel is then either quenched directly from the box, or is allowed to cool without unpacking, and finally given a single hardening-heat., or, for special work, two or three heats. During the year 1911, more than 100,000 tons of carbonizing-material was sold in the United States, at an average price of probably $55 per ton. More than 85 per cent. of this material consisted of granulated bone. Within the past four years, many manufactured compounds have been placed on the market, consisting largely of some form of carbon or carbonaceous material, with or without the addition of chemicals. Steel will absorb carbon placed in contact with it at the temperature of the atmosphere. The reaction is exceedingly slow, but. increases rapidly with increasing temperature. Below * Metallurgical Engineer, The Peerless Motor Car Co.

Dec 1, 1912

By Richard E. Chism

If internal commotion can be called life, the Mexicans have certainly lived more in the last seventy-five years than any other people. To the oppression of the Spanish viceroys succeeded the sanguinary tumults of the Revolution of Independence, after which the Supreme Congress bequeathed its heritage of uncertain power to the empire of Iturbide, the only one ever established by Americans upon American soil, with an American at its head. That shortlived reign mas followed by years of ceaseless, bloody, and, to the superficial observer, meaningless revolutions—the deeper political and ecclesiastical significance of which it is beyond the scope of this paper to discuss. Then came foreign intervention, the ill-fated Austrian's brief supremacy, and the final triumph of the patriot cause under rugged old Benito Juarez, who crowned the victory of arms by a series of reforms breaking forever the temporal power of the Church and ushering in the calmer era which has lasted from the first accession of Diaz to the present day. During all those troublous times, the revolutionary ocean, that rolled so deeply over all other relics of Spanish dominion, had left almost unaltered the ancient laws of Spain, still lifting themselves above the tide, like landmarks of a flooded world. Many of these laws were obsolete ; some were absurdly inadequate to the demands

Jan 1, 1886

By J. D. Anthony

The Australian continent possesses significant reserves of a wide range of minerals, including bauxite, coal, copper, diamonds, gold, iron ore, lead, manganese, mineral sands, nickel, phosphate, silver, tin, uranium, and zinc. Australia's identified economic resources of many minerals are very large as indicated in Table 1. A sophisticated and highly experienced mineral industry is now an established feature of the Australian economy and Australia is the world's largest exporter of iron ore, alumina, mineral sands and refined lead and amongst the leading suppliers of many other commodities such as coal, lead and zinc ores/concentrates, nickel, refined zinc, tungsten concentrates and bauxite. The industry exports 70% of its production. This is reflected in the value of Australian mineral exports which have grown from about $200m in 1960/61, comprising 10% of total export receipts, to about $1265m or 29% of export income in 1970/71 to around $7061 representing 37% of Australia's total export income in 1980/81. Details of the more significant minerals are as follows: Japan (42.1%) USA (11.3%) ASEAN (6.3%) UK (5.9%) F.R. Germany (3.8%) Republic of Korea (3.4%) New Zealand (2.6%) Also see Table 2. AUSTRALIA'S MINERAL RESOURCES POLICIES Federal and State Governments' Responsibilities Australia has a federal system of government comprising six States, a self-governing Territory and a Federal Government. Under the Australian federal system the Constitution sets down the powers of the Federal Government. All powers not assigned to the Federal Government in the Australian Constitution reside automatically with the States. Certain of these broad powers result in the Federal Government having a significant influence on resources development. For example, in being responsible for economic management, the Federal Government's fiscal and monetary policies have an important effect on industry as well as on State finances. In particular, the taxation regime employed by the Federal Government is of direct importance to decision-makers in the resources industry. The Federal Government is responsible also under the Constitution for external trade matters; and international trade and commodity matters are increasingly important in Australia's international relationships. Foreign investment is another area where the Federal Government has a role to ensure that national interests are protected. This foreign investment power flows from the Federal Government's control of foreign exchange movements into and out of Australia. However, before enlarging on these and others of the Federal Government's powers and policies, it should be emphasized that the State governments, by virtue of their wide powers to regulate matters within their own boundaries, are more directly involved in the day-to-day administration and regulation of mining operations. For instance, the powers of the State governments include the responsibility-for the granting of exploration rights and mining leases, the approval of mining operations and the levying of royalties and other like charges. Administrative arrangements covering the granting of minerals and petroleum exploration and development titles vary from State to State. Before development rights are granted, State governments consider environment protection and rehabilitation aspects of development proposals. The provision of infrastructure within State borders is a matter primarily of State government responsibility. It is usual practice in Australia for State governments to construct and operate infrastructure services such. as railways, ports and electricity generation and transmission. The States may also provide certain public services such as electricity. and water, port and loading facilities, communications, health and education services which form part of the infrastructure of mining operations. In remote areas the mining companies themselves usually are expected to provide much of this infrastructure. However, the Federal Government is primarily responsible in some fields, such as telecommunications and parts of the railways network. State governments carry out preliminary exploration and geological mapping and some are directly involved in the mining of coal for power generation. The Federal Government's responsibilities in addition to economic management, taxation, international relations, foreign capital and investment, include regulation of exports, environmental matters and matters affecting the Aboriginals of the Northern Territory. FEDERAL GOVERNMENT POLICIES The continued sound development of the minerals and energy resources sector is regarded by the Federal Government as being of very great importance. However, the Government does not seek to participate directly in resource developments. It sees its role rather as that of establishing a sound economic and policy climate in which private companies can identify opportunities, seek out customers and marshall the necessary capital for the development of resource projects.

Jan 1, 1982

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By Edward Keller

Jan 1, 1906

By K. A. Gschneidner, O. D. McMasters, T. J. O’Keefe

X-ray diffraction, differential thermal, ad rnetallo-graphic methods were used to establish the Dy-Pb Phase diagram. Lead additions lower the 1377°C transformation temperature of dysprosium to 1360°C leading to an inverted peritectic reaction. The 327°C melting point of lead is lowered by dysprosium additions to about 326°C yielding a eutectic reaction. A second eutectic reaction occurs at 13.3 at. pct Pb and 1200°C. The dysprosium-richest intermetallic compound DysPb3 melts congruently at 1695°C and crystallizes in the hexagonal Mn5Si3 (D8,) type structure. The peritectic decomposition temperatures for the remaining compounds are Dy5Pb, at 1555C, DyPb2 at 955C, and DyPb3 at 880°C. A fifth compound near the DyPb stoichiometry exists over a 310°C temperature range decomposing at 1130°C by means of an inverted peritectic reaction and melting incongruently at 1440°C. The crystal structures of the compounds are discussed. A systematic study of the rare earth-lead alloy systems is underway in an effort to supply information concerning the alloying behavior of the rare earth metals. The Dy-Pb phase diagram is the fourth system to be investigated in this study. The Yb-Pb,1 Y-Pb,2 and Eu-Pb 3 diagrams have been published recently. Utilization of the rare earth series of metals as a research tool in this manner should yield a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The lead used in this investigation was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The dysprosium was prepared in this Laboratory by the calcium reduction of the fluoride followed by distillation of the dysprosium. The major impurities in the dysprosium in ppm are: A1 (<40), Ca (400), Er (<50), Gd (<200), Ho (<200), Mg (<50), Si (30), Ta (400), Tb (<100), Y (<50), 0 (651, H (15), N (not detected), F (430), C (35). Alloy Preparation. Most of the alloys were prepared by melting weighed amounts of dysprosium and lead in sealed tantalum crucibles. The tantalum crucibles were sealed by are-welding in a He-Ar atmosphere welding chamber. Thus the alloys are in contact with He-Ar at about 1 atm pressure. Homogenization was achieved by holding them in the liquid state for about 1 hr, cooling, inverting the crucibles, remelting, and repeating the process at least twice. Since these alloys were prepared in sealed tantalum crucibles, chemical analysis for final composition was thought to be unnecessary. No detectable reaction of these alloys with the tantalum crucible was observed by metallographic examination. Metallographic evidence was also used to confirm the homogeneity of some of the alloys prepared in this manner. The compositions of a few alloys, which were prepared by nonconsum-able are-melting, were corrected for the small weight losses involved by assuming that the weight loss is due to vaporization of lead. The specimens obtained from the alloy samples were prepared under a dry-argon atmosphere because they were rapidly attacked by air and moisture. Thermal Analysis. Differential thermal analysis methods were used to determine the liquidus curves and reaction horizontals of the system. Both Pt vs Pt + 13 pct Rh and W + 5 pct Re vs W + 26 pct Re thermocouples were used to measure the temperature. An X- Y recorder was used to record the specimen temperature and differential electromotive force between the specimen and molybdenum standard. The arrest temperatures were measured potentiometri-cally. The accuracy limits (* values) associated with the reaction temperatures obtained by this method were estimated on the basis of both the reproducibility of the particular temperature value and the accuracy of the thermocouple at a given temperature. Liquidus temperatures were obtained from cooling arrest data while both heating and cooling arrest data were used to establish the horizontals of the diagram. Heat treatments during the thermal analyses of the alloys between 40 and 70 at. pct Pb were necessary in order to approach equilibrium conditions. The samples were held at temperatures between the various peritectic horizontals for l to 2 hr before the thermal analyses were continued. The entire range of compositions was investigated at the expense of a minimum amount of materials by adding appropriate amounts of lead to master alloys. More than sixty alloys were analyzed by this differential thermal method and for each alloy the results given herein are taken from two or three heating and cooling cycles. X-Ray and Metallographic Methods. Slice specimens for metallography and powder specimens for X-ray diffraction were prepared from rod-shaped samples which had been melted in sealed 0.62 5-cm-diam tantalum crucibles. The specimens were heat-treated in sealed tantalum crucibles which were protected by sealing them in argon-filled quartz ampules. Quenching was accomplished by breaking the ampules in ice water after heat treatment. X-ray powder specimens were sealed in 0.3-mm-diam glass capillaries under a dry-argon atmosphere. Copper, iron, and chromium radiation were used to obtain the powder patterns for these alloys. More than 150 powder patterns were obtained for specimens of various compositions and heat treatments. Included in these were several patterns for specimens which had purposely been oxidized. Patterns from specimens which had been accidentally exposed

Jan 1, 1969

By B. E. Thompson, H. B. Fuqua

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T&apos;his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By H. B. Fuqua, B. E. Thompson

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T&apos;his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By R. S. Wagner, W. G. Pfann

If an electric field is applied to a conducting liquid solution, changes in concentration usually occur because of differences in ionic mobilities. A variety of ways of utilizing this effect in conjunction with the freezing process are discussed in principle. For example, if a column of binary eutectic liquid is maintained a few degrees above the melting point and a field is applied, the component solid solutions will crystallize at opposite ends of the column until the liquid is consumed. An expression for the effective distribution coefficient, k, is derived for the case of a direct current Passing through a solid-liquid interface. It is shown that k can be varied It is well known that solute distributions in crystalline substances can be controlled by careful freezing from melt or solution. It is also well known that an electric field can produce substantial changes of concentration in liquid solutions by virtue of differences over a wide range, including values outside the usual range between ko (the equilibrium value) and unity. Hence, for many systems: the efficiency of zone refining can be increased; a ko of unity can be made greater or less than unity; solutes that lower or raise the fretzing point can be concentrated at the same end of the ingot by zone refining; be made equal to unity; and the tendency toward constitutional supercooling can be reduced. The methods of field-freezing are applicable to a wide range of materials including metals, semiconductors, and ionic conductors. in ionic mobility. In this paper we discuss, in principle, some methods that combine these techniques in useful way&apos;s. The methods are designated by the general term, field-freezing. Topics discussed include separation of the components of a eutectic, crystal growth, and controlling the value of the effective distribution coefficient. The methods are applicable to a broad range of materials, including alloys, semiconductors, fused salts, and other liquid electrolytes.

Jan 1, 1962

By Otto W. Nuttli

THE magnetic method of prospecting is well suited to determination of faulting in the basement rock. In addition to establishing the horizontal position of the fault, it often furnishes valuable information concerning the depth and amount of faulting. Consider a simple case of a vertical fault, represented in cross-section in Fig. 1. Let A A&apos; represent the plane of observation (ordinarily the surface of the earth), and BB&apos;B"B"&apos; the upper surface of the basement. Assume that the sedimentary rocks are nonmagnetic, so that the magnetic susceptibility of the material above the basement is zero. Let k indicate the susceptibility of the basement rock, c the density contrast between it and the neighboring sedimentary rocks, and the amount of vertical displacement. Fig. 1 shows the material, indicated by cross- hatching, which gives rise to the magnetic anomaly. In most cases it can be assumed that is small compared to the thickness of the sedimentary rocks. The semi-infinite, rectangular slab of rock of susceptibility k, density contrast , and thickness t may then be replaced by a semi-infinite sheet CC&apos; of mass t per unit area at depth 2 (the mean depth of the slab). Nettleton 1 states that this approximation results in an error of less than 2 pct for the computed gravitational field intensity when t is as great as 2/2 and decreases rapidly for smaller values of t. By a theorem of Poisson, the magnetic field intensity can be determined readily from the gravitational field. The theorem states that W = (I/) • (U/i) i1 [1] where W is the magnetic potential associated with the structure, I is the intensity of magnetization which is assumed to have the direction of the inducing field, ? is the constant of gravitation, the density contrast, U the gravitational potential associated with the structure, i the direction of the inducing magnetic field, and i1 a unit vector in that direction. The multiplication indicated in Eq. 1 is

Jan 1, 1956

NEW MEMBERS The following list comprises the names of those persons who became members during the period of July 10, 1917, to Aug. 10, 1917. ARNOT, STANLEY L., Engr., Plymouth Cons. Gold Mines; Ltd., Plymouth, Amador Co .2 Cal. BARRETT, LESLIE PARK, Asst. Geol.... Michigan Geological Survey, Lansing, Mich. BENNIE, JOHN WILLIS Gen&apos;l. Mgr., Shannon Copper Co., Clifton, Ariz. BRINTON, OWEN FUGATE Mgr., Admiralty Zinc Co., Quapaw, Okla. BRODERMANN, JORGE, Civil Engr., Compania Minera San Francisco, Havana,Cuba. BROWN, RICHARD HENRY JR., Sales Engr., Ingersoll Rand Co., 300 N. Broadway, St. Louis, Mo. BROWN, STANLEY Chile Exploration Co., Chuquicamata, Chile. BUDDECKE, WILLIAM A Pres., Point Milling & Mfg., Co. Mineral Point, Mo. BURGESS, GEORGE K., Physicist and Chief, Division of Metallurgy, Bureau of Standards, Washington, D. C.

Jan 9, 1917

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948