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By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8.9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3-s in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6.9 The measure of internal friction adopted here, I/Q, is (p) X the logarithmic decrement, a measure used by some writers, and is also (I/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°°C. As shown in Fig. i, the internal friction increased by only a factor of 2 from room temperature to 300°°C., then by a factor of 100 during the next :too' interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction ~ e-HI/RT [I]

Jan 1, 1942

By John A. Church

Jan 1, 1903

By R. C. Philp, Allan Gibb

INTRODUCTION. THE term matte is applied to smelting-products so extremely diverse in composition and physical properties that it appears impossible to devise any generic formula to represent, chemically, the manner in which the varied proportions of the almost unlimited possible constituents combine with each other. Mattes produced in copper-smelting, in distinction from those produced in smelting-operations in which the recovery of copper is secondary to that of other metals, cover a narrower range in composition. The copper-content of such mattes vary from 20 to 80 per cent., and even this range is much smaller in general practice since it is found advantageous, when possible, to produce mattes with about. 50 per cent. of copper in the first operation. Further, it is unusual that arsenic or antimony occurs in copper-ores in sufficient proportions to form arsenides or antimonides in such quantities that they will separate out from the furnace-products, as is common in lead-smelting. Generally, the mattes produced in copper-smelting are composed mainly of copper (usually greater than 35 per cent.), iron and sulphur, the remaining elements being usually in proportions sufficiently small to allow of their treatment as impurities, rather than as essential constituents of the mattes. In modern practice of smelting copper-ores in blast-furnaces the tendency is to approach pyritic smelting as nearly as pos¬sible, the furnaces being low and the air supplied being largely in excess of that required for complete combustion of the carbonaceous fuel. Hence the atmosphere of the blast-furnace thus used is usually oxidizing or Dearly neutral? and, as a consequence, the reduction of metallic iron that was a necessary evil of former practice is of unusual occurrence in operations where the main object is the recovery of copper. Hearth-accre-

Nov 1, 1905

Paper withdrawn from publication September 8,1977, after book was printed. Pages 258.272 are therefore omitted.

Jan 1, 1977

By John D. Welsh

Jan 1, 1985

By B. B. Zavoico

During 1936 the Russian oil industry made very satisfactory progress and, while not all difficulties of organization have been ironed out, the country is now assured of a supply of petroleum products in sufficient quantities and of quality demanded by modern motor equipment. The year 1937 promises to better by a wide margin the good showing of 1936. The statistics given in this paper for the first time take into consideration the varying gravities of crude oils of the several Russian oil fields instead of using a flat conversion factor of 7 bbl. per metric ton. It was found from the detailed study that the generally used average conversion factor should be increased from 7 to 7.25 bbl. per metric ton, the figure varying, of course, with the gravity of oil in the individual fields. Crude-oil production during 1936 is estimated at 201,500,000 bbl. as compared with 182,970,000 bbl. produced in 1935, an increase of 9.4 per cent. The greatest increase was again recorded in the Baku district, which increased its production by 10.9 per cent, from 141,257,000 bbl. in 1935 to 158,300,000 in 1936. Grozny district maintained its production at a level of about 23,000,000 bbl., but its old fields continued to decline and production was sustained by the development of newer fields. A great advance was made in drilling speeds and the total footage in 1936 reached 6,694,200 ft. as compared with 4,926,600 ft. drilled in 1935, an increase of 26.4 per cent. In older deep fields, producers were being completed at over 8000 ft.—a great depth for Russian drillers but two years ago. Several major discoveries were made in 1936. Northeast Caucasus.—Izberbash, east from Grozny and on the Caspian Sea, was the outstanding discovery, the initial production of the discovery well being around 3000 bbl. per day from about 5000 ft. The importance of the field is due to the large area of the structure, half of which, however, is under the sea, and also to its strategic location on the shores of the Caspian and near a trunk pipe line to the Grozny refining center. An active development program is being pursued in Izberbash and its 1937 production quota is set at 7,500,000 bbl. Achi-Su field, near Izberbash, also discovered during 1936, while not as prolific as Izberbash, is thought to cover a very large area and the small

Jan 1, 1937

By Basil B. Zavoico

PRODUCTION of crude it in the United States during 1939 totaled about 1.255,776,000 barrels, an average of 3,440,482 barrels per day, 3.41 per cent above the 1938 output of 1,214,355,000 barrels but 1.83 per cent below the record pro¬duction of 1,279,160,000 barrels, in 1937. However only the two-week shutdown of oil fields in the Southwestern States in August and September prevented the domestic crude production from establishing an all-time record in 1939. Demand for all petroleum products for the first ten months of 1939 showed an increase of 7.04 per cent over the similar period of 1938. Domestic demand for all petroleum products was particularly benefited by the increasing industrial activity, advancing 8.37 per cent above the like period of the preceding year equivalent to a volume increment of 256,810 barrels per day; with motor-fuel demand gaining 5.83 per cent and demand for all fuel oils gaining 12.15 per cent over the corresponding period of 1938. The export demand for the first ten months of 1939 was slightly below the export movements during the same period of 1938, declining 0.56 per cent. The European war was a major factor in 1939 for the petroleum industry in the United States, even if, at the end of the year, the war had not yet resulted in the expected large shipments to England and France.

Jan 1, 1940

By Thomas T., Read

IT will be recalled that the first professor of metallurgy in the United States, appointed in 1855, never really gave any instruction in metallurgy and gradually turned into a professor of mineralogy. Metallurgy was included with. mining in the early curricula, two students who took the B.S. in mining engineering from the Polytechnic College of Pennsylvania in 1862 wrote their graduation theses on the metallurgy of copper and zinc, respectively. Even after Columbia School of Mines established, in 1868, a separate curriculum leading to the Ph.B. degree in metallurgy, very few students elected it,* preferring to take the mining degree, since they received in its curriculum nearly all the metallurgical instruction they would have in the metallurgical curriculum. For many years a large proportion of the men who attained prominence in metallurgical enterprises had taken mining rather than metallurgical degrees. METALLURGY Clifton Sorby's study of thin sections of rocks under the micro¬scope, beginning in 1850, and its subsequent development by Zirkel and others, had made microscopic petrography a recog¬nized department of geological research as early as 1873. . It was inevitable that the idea of studying polished metal surfaces-¬under the microscope by reflected instead of transmitted light would occur to investigators. Sorby himself did it in 1864, and Adolph Martens and Floris Osmond may -be especially named among the many European workers who, by the late eighties, had so developed the, necessary techniques that they were able to photograph polished metal surfaces at magnifications as high

Jan 1, 1941

By Russell A. Carter

Seven years of rising silver prices have effectively revived an historic Idaho mining district and given it a new lease on life. Initial production earlier last year from the DeLamar open-pit silver mine in southwestern Idaho ushered in a new era of mineral production in a region that has weathered boom-and-bust cycles reaching back the better part of a century.

Jan 1, 1978

By A. T. Yu

As the first loads of Noamundi iron ore rumbled into the new 54-in. Gyratory Crusher on March 30, 1968, one of India's largest and most modern iron ore processing complexes began operations. The completion of the $13 million mining and processing complex brought to a successful conclusion the second chapter of a phased expansion program initiated in 1958 by India's gigantic Tata Iron and Steel Co. The completed complex will yield annually 2.5 million tons of washed, sized ore and sinter fines destined for Tata's furnaces at Jamshedpur. Hewitt-Robins Div. of Litton Industries was awarded the turnkey project on the basis of world- wide competitive bids. Eighty miles southwest of the city of Jamshedpur, Noamundi lies on an approximate geographic grid of 22º-5' latitude north and 85º-30' longitude east. The mine is approximately 600 ft above sea level.

Jan 11, 1968

By C. R. Kuzell

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: C. C. Long, President; John Chipman, Past-President; J. S. Smart, Jr., Vice-President, T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMiTTEE OF THE METALLURGICAL SOCIETY: D. J. Carney, Chairman; Robert Maddin, Past-Chairman; J. H. Hollomon, J. H. Jackson, H. H. Kellogg, T. B. King, F. C. Langen-berg, D. L. McBride, W. O. Philbrook, J. S. Smart, Jr., R. L. Smith, J. D. Sullivan, and F. L. Vogel Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: H. H. Kellogg, Chairman; T. 8. King, Post-Chairmon; R. P. Hermsdorf, W. A. Krivsky, R. E. Lund, C. L. McCobe, Poul Queneou, A. 5. Russell, M. E. Wadsworth, and W. D. Wilkinson. Institute of Metals Division: R. L. Smith, Choirman; P. A. Beck, I. I. Bessen, J. O. Betterton, Jr., R. S. Davis, J. J. Gilmon, R. 8. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurlond, J. J. Heger, M. Hermon, J. N. Hobstetter, H. H. Johnson, Jr., I. R. Krarner, W. C. Leslie, R. A. Meussner, R. R. Nosh, G. E. Pellissier, T. N. Rhodin, A. U. Seybolt, L. L. Seigle, I. S. Servi, P. G. Shewmon, L. Slifkin, J. K. Stanley, C. D. Starr, and J. Washburn. Iron and Steel Division: F. C. Longenberg, Chairmon; H. L. Bishop, C. W. Sherman, J. 8. Wagstaff, and E. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for nan-AIME members in United States and North, South, and Central America; $25, foreign; $5 far AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1960 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ...Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts ... Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 218, Number 4

Jan 1, 1961

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By J. J. Predali, J. M. Cases

J. J. Predali and J. M. Cases (Attachè de Recherche and Charge de Recherche, respectively, Centre de Recherches sur la Valorisation des Minerais, Institut Polytechnique de Nancy, Nancy, France)-The role of CO, in carbonate flotation is one of the parameters of a complex phenomenon: the adsorption of salts of fatty acids onto minerals. The authors therefore must be congratulated for their work. Their experimental results suggest some questions: 1) Recovery with C02, benzoic acid, or HCl, look very similar [(Fig. 1)] to that with the use of air; however, the recovery decreases very slightly (<10%). But in these two kinds of experiments, two parameters are different: the pH which is near 5.8 (with C02) becomes 9.1(without C02) and the concentration of Ca* I x 10-3 mole per 1 (without C02) becomes 1.9 X 10&apos; mole per 1 (without COO. 2) Adsorption experiments (Fig. 2) permit computing the surface coverage 9 which is 7.4% (without C02) and 8% (without CO_.) for an initial concentration of 12 X 10-6 mole per 1 in sodium oleate. It seems doubtful to us that this small variation can produce large increases of the recovery in flotation. 3) It is difficult to correlate adsoption and flotation experiments because they do not seem to have been done with the same size of particles. The concentration needed to obtain 95% recovery (Fig. 1) is about 3.0 X 10_" mole per l, that is, 1.13 X 10-6 mole for about

Jan 1, 1973

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine&apos; quantity of crude and distillate reserves added in &apos;943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area&apos; Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine&apos; quantity of crude and distillate reserves added in &apos;943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area&apos; Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944

By H. J. Ramey, I. S. Bousaid

Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsoli-dated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. INTRODUCTION The production of crude oil by underground combustion has been studied in the laboratory by many investigators.1-5 Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investiga-tors5-9 have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish10 demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema11 presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on the reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., 12 studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe13 noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and it accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al.,14 studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. One

Jan 1, 1969

By J. P. Hirth, A. H. Clauer

A simple graphical method is presented for the determination of climb forces on dislocations exerted by uniaxial stresses. In conjunction with standard stereographic projections, the technique is applicable for any crystal system. Climb forces on glide dislocations in bcc crystals are determined as an application. In connection with a study1 of elevated temperature creep of molybdenum single crystals, a detailed analysis of the climb force on a dislocation was necessary. In general, such forces can be calculated for an arbitrary dislocation segment from the Peach-Koehler equation2 (or one of its variants3"6) where Fk are the components of the force per unit length of dislocation line, ?i of the unit sense vector tangent to the line, ojl of the stress tensor, bl of the dislocation Burgers vector, and is the Einstein permutation operator with components ?123 = ?231 = ?321 = —?132 = — ?321 = —?—213 = unity, and all other components zero. It is understood in the suffix notation of Eq. [I.] that repeated indices are to be summed over 1, 2, and 3. For the most general coordinate system, the matrix manipulations required to solve Eq. [I] are fairly complex. However, a simplification can be achieved by specifying a coordinate system based on the dislocation in question. The pertinent system involves cartesian coordinates xi, x;, xi, with attendant unit vectors e&apos;i; ei being parallel to the Burgers vector b, and e&apos;3; being parallel to the climb directions (b x ?), i.e., normal to the slip plane. In this coordnate system b = (bi, 0, 0) and ? = (?&apos;1,?&apos;2, 0). Hence, Eq. [I] yields for the climb force per unit length F3 = ?&apos;2s&apos;11b&apos;1—?&apos;1s&apos;12b&apos;1 [2] The first term on the right side of Eq. [2] is the climb force on the edge component of the dislocation, while the second is the (cross-slip) force normal to the glide plane acting on the screw component. Thus, the problem of determining the climb force reduces to that of resolving the stress components —il and s&apos;12 in the xi coordinate system. Several authors7- l0 have shown, for the glide case, that such stress resolution can be performed most readily by graphical methods. Therefore, we present a similar method for the climb case. Of the suggested methods, we follow that of Hartley and Hirth,9 which can be performed directly with a standard stereographic projection for the crystal system in question. We treat the case of simple tension, or compression, this being the most common creep test in which climb is important. A set of cartesian coordinates (x1, x2, x3) is fixed with x3 parallel to the specimen axis. This set is connected to the x&apos;i set by the factors defined in Table I. A perspective view of the coordinate systems relating them to the glide ellipse, is given in Fig. 1, while a stereographic projection of the coordinate systems is presented in Fig. 2. The transformation matrix connecting the xi and xi coordinates is x&apos;i =aijXj [3] where an a11 a13 aij = a21 a22 a23 a31 a23 [4] s The corresponding transformation for the stresses is i [5] The only nonzero component of okl for the simple tension case is s33,. Hence, using Eqs. [4] and 151, we find that Eq. [2] becomes F3 = b&apos;1s33 sin2 cos ?[cos ? sin a - sin ? cos a] [6] = m1b&apos;1s033 sin a- rn2b&apos;s33 cos a where sin a = 5: and cos a = ?i, with a the angle measured from b to ?, i.e., a polar angle in the x1, x2 plane. The same equation with a sign change applies for compression. A graphical plot of the "Schmid" factor m1, relating to the climb force on the edge component, is presented in the stereographic projection of Fig. 3. In this projection the glide plane normal points toward the top of the page and the glide direction points normal to the plane of the page. To use the graph, one

Jan 1, 1970

By R. F. Mehl, C. E. Birchenall

SINCE Maxwell1 first considered the self-diffusion process in 1872 its importance in the kinetic theory of matter has been recognized. Until the discovery of isotopes in 1913, a direct measurement of this quantity seemed impossible. The only information that could be gathered indirectly was for gaseous systems for which the kinetic theory was well developed. When methods of direct observation be-came available, investigations on self-diffusion were carried out in condensed phases. In metals these data are presumably of potential importance in the study of recovery, recrystallization, creep, sintering, and related phenomena. Following the pioneer work of Von Hevesy2 and his collaborators, who determined the rate of self-diffusion in lead with the naturally occurring thorium B isotope, several metals have been investigated. Pb, Ag³, Au.6,5, and Cu6,7,8,9 are examples of isotropic crystals existing in only one phase modification. Anisotropy of diffusion has been demonstrated in Bil6 and Znll. This paper is a study of a single metal in two allotropic forms and also of self-diffusion in a body-centered cubic lattice. Despite the fact that the measurements in each of the papers cited on self-diffusion in copper seem to be internally consistent to about 10 to 15 pet, the curves reported by different authors differ by factors of 2 to 4 at the same temperatures. This uncertainty may account, in part, for the failure to establish a successful correlation between the self-diffusion rates and other physical characteristics of the metals. No satisfactory theory of metallic self- diffusion has as yet been proposed to account for all the existing data and to permit estimation in other metals. Experimental Part: Two units of radioactive iron were used in these experiments, each a mixture of Fe53 and Fe59 (12). Fe53 decays by K electron capture and the emission of an X ray with a half life of about 4 years. Fe59 emits two beta spectra, one with a maximum energy of 0.26 Mev, the other 0.46 Mev, and gamma rays of 1.1 and 1.3 Mev, with a half life of about 44 days. They were present in nearly equal concentration initially. The composite half life started at about 50 days and increased as the Fe59 decayed, leaving Fe55 relatively more abundant. After aging a year, the half life was too long to measure significant decay in a month. The absorption properties also changed with time. Because of the importance of the absorption coefficient in the diffusion calculations, it was necessary to determine this quantity frequently over the period during which these experiments were carried out. This correction was unsuspected at the time of publication of notesl3 on this work and accounts for the discrepancy in alpha iron and for part of the discrepancy in gamma iron.* * The data in the present paper supersede those given in the notes entirely. In one note the scale of log D was inadvertently reversed. In addition to the correction for the drift in absorption coefficient, the D values for gamma iron at low temperatures were high owing to insuficient correction for diffusion occurring during heating and cooling through the high temperature part of the alpha range at a rate much slower than that employed in the runs reported here. The high temperature alpha rates are much higher than the low temperature gamma rates and correspond to large equivalent times at these temperatures. These experiments were discarded and new measurements taken. Independent experiments with the same activity units indicated a radioactive contaminant in the iron, but exhaustive attempts to isolate and identify it chemically failed. These experiments? indicate † These experiments will be discussed in a later publication from this laboratory. that the contaminant represented only a trace of little importance in the diffusion results. The active iron was plated from an iron chloride solution. Enough of the solution was dropped on a 1% in. square of filter paper to wet it thoroughly.

Jan 1, 1951

By F. R. Morral, K. T. Aust

The preferred orientation and earing characteristics of ZS aluminum were studied. An empirical correlation was obtained relating earing behavior and variation of mechanical properties for face-centered cubic metals. Strain-ratio mecsurements for ZS were found to be in good agreement with Hill&apos;s theory of plastic anisotropy. DIRECTIONALITY in sheet metals may be revealed by earing in a cupping test, or by the variation of mechanical properties of tensile specimens taken at different angles to the rolling direction. However, no simple correlation appears to exist between earing and variation in mechanical properties in metals and alloys studied.1-5 Aluminum of commercial purity (known as 2S, with a specified minimum of 99.0 pct Al) cast by the direct casting process was chosen in the present investigation since ears at 45° or 0°, 90° can readily be obtained. Preferred orientation is often the principal cause of uneven metal flow, such as earing, and variation in mechanical properties. Consequently, the preferred orientation characteristics of 2s aluminum were initially studied using both X-ray diffraction and micrographic techniques. The variation of mechanical properties with angle to the rolling direction was next determined in an effort to clarify the apparent lack of correlation of earing behavior with mechanical properties for face-centered cubic metals. Strain-ratio*5,8 measurements were finally conducted to determine first, if the maximum values of the strain ratio occurred at the earing positions, and second, if Hill&apos;s theory of plastic anisotropy7 is applicable to other face-centered cubic metals such as aluminum. Detailed treatments, working, and heat treating are not given in this paper since this study is not concerned with the methods to produce earing, but to correlate earing with other properties and characteristics of the material. The percentage of earing was measured using the formula specified by the x—Y Aluminum Association, -------- X 100 = pct earing, where x is the height of the ear and y is the height of the valley from the bottom of the cup. Preferred Orientation Characteristics of 2S X-ray Studies: Beck and coworkers8 have determined that the rolling texture of 2s after 95 pct cold reduction may be approximately described by four equivalent ideal orientations near (123) [121]. Also, the recrystallization or annealing texture of 2s aluminum consists of four components of the (123) [l21] type, retained from the rolling texture, and of a (100) [001] or cube texture component." Fig. 1 illustrates the typical appearance of deep drawn earing cups with the corresponding X-ray diffraction patterns. The X-ray patterns were taken with copper radiation using the structure-integrating method&apos;" in which the specimen is scanned during the X-ray exposure. The rolling direction was vertical and the rolling plane was perpendicular to the horizontal X-ray beam. It was found that an increase in the retained rolling texture component resulted in a greater 45" ear height, while an increase in the recrystallization texture component (i.e., cube texture) caused greater 0°, 90° earing. X-ray diffraction studies of 2s cold rolled to final thickness followed by a final anneal have shown that the rolling texture, and also the retained component of the rolling texture after annealing, are increased with greater cold-rolling reduction. The preferred orientation characteristics of 2s sheets given an intermediate anneal between cold rolling followed by a final anneal were found to depend on the position of the intermediate anneal during cold rolling. For instance, three identical samples of 2s homogenized ingot, each 1 in. thick, were given the following cold-rolling and annealing treatments: 1—50 pct reduction, intermediate anneal, 96 pct reduction to 0.020 in. and a final anneal; 2—75 pct reduction, intermediate anneal, 92 pct reduction to 0.020 in. and a final anneal; and 3—90 pct reduction, intermediate anneal, 80 pct reduction to 0.020 in. and a final anneal. The intermediate and final annealing treatments consisted of a 70°F per hr heating rate, held 6 hr at 800°F and air cooled. Typical X-ray patterns after each of these treatments are shown in Fig. 2. It was evident that after treatment 1, the retained rolling texture component predominated; after treatment 2, the retained roll-

Jan 1, 1954