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By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick's first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)'/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.' , ' Regarding mass transport through dense solid oxide layers, Wagner' has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.' Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work', 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-'" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956

THE refining period of an open-hearth heat blends imperceptibly into the finishing period, during which final adjustments are made in slag composition, in bath action and temperature, and in composition of the steel, in order to prepare it for casting into ingots. Operations must be governed by the consideration that alterations in the character of the heat during the finishing period must be held to a minimum. In a broad sense, the finishing and deoxidation period of a heat may be said to begin when the action of the last ore addition has ceased, and to end when the teeming of the ingots is completed. INGOT STRUCTURES A survey of the relative advantages and disadvantages of different types of ingot structure is required because deoxidation treatments during the finishing period control the amount of gas evolved during solidification and consequently determine the type of ingot structure. Four classes of ingots are recognized, depending upon the degree of deoxidation to which the steel has been subjected. These types are killed, semikilled, capped, and rimmed; typical examples of their structures are represented by ingots 1, 2, 5, and 7, respectively, of Fig 9-1. The actual ingots from which these cross sections were sketched were all poured to the same height (indicated by the dotted lines) in the same type and size of bottle-top molds. The eight drawings of the figure represent selected types of ingot structure in a continuous series from "dead killed" to "wild," resulting from variations in the total quantity of gas evolved, from none at all to copious amounts, during solidification of the steel in the mold. Killed and semikilled steels are adjacent at the "quiescent" end of the ingot structure series where only small amounts of gas are evolved. The term "quiescent" describes the action of the molten metal during and subsequent to the teeming of killed and semikilled steels. Capped and rimmed steels are adjacent at the

Jan 1, 1951

By William Priestley

IN THE manufacture of gun forgings and other steel parts that, in service, are subject to sudden high stresses and shocks, it is most desirable to use steel possessing the greatest toughness and ductility possible without sacrifice of strength. In order to obtain this condition, it is necessary to procure steel that shows the highest possible elongation and reduction of area without lowering the tensile strength and elastic limit. Proper heat treatment of the steel can control this condition within certain limits. When heat treatment has failed to produce the desired results, metallurgists have used steels containing molybdenum, zirconium, vanadium, chromium, tungsten, etc. The purpose of this paper is to describe a method by which these desired physical properties may be procured-by the elimination of certain impurities that inherently exist in steel made by the open-hearth process, and without the use of expensive alloys. DESIGN OF GUN FORGINGS In the manufacture of gun forgings, a certain elastic limit is fixed by the designer, and the walls of the gun are made of the proper thickness, allowing a suitable factor of safety for the high stresses and sudden shocks that occur during gun firing. The elastic strength of the gun is about 1.4 times the stress set up at any point along the bore of the gun during firing with the maximum powder charge.

Jan 12, 1921

By W. M. Weigel

SALT production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open 'kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been estimated only by geophysical methods. The diameter of the salt core varies from less than ½ mile to over 2 miles. Only domes where the salt is compara-tively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use.

Jan 1, 1935

By F. W. Newhall, L. N. Plein

During the latter part of the year 1931, the Republic mine of the Republic Steel Corporation, at Republic, about 4 miles south of Brownsville, Pa., was mining coal along four rib or fracture lines. One of these lines, the west butt rib line, was retreating towards a concrete-lined air shaft, 320 ft. deep, which had been sunk in 1911 for ventilation purposes. With the normal rate of mining at that time, it was expected that this rib line would pass the shaft in three or four months and the shaft would then be abandoned and allowed to cave. Realizing the opportunity presented for the study of an unusual case of ground movement, the question of conducting the study was presented by the junior author to thechairman of the Institute's committee on Ground Movement and Subsidence, Mr. George S. Rice, who presented the matter to Mr. G. H. Morse, General Manager of the Northern Mines, Republic Steel Corporation, and he agreed to cooperate with the Bureau of Mines in making the study, the results of which arc presented in this paper. Acknowledgments are due to Mr. Morse for his full cooperation in this work and to Mr. G. S. Rice and Mr. J. W. Paul, both of the U. S. Bureau of Mines, for their advice and guidance during the course of the work. The authors are indebted to Mr. B. F. Herbert, mining engineer, Northern Coal Mines, Republic Steel Corporation, who assisted in all the surveys, and Mr. W. H. Smith, draftsman, U. S. Bureau of Mines, who prepared all illustrations for publication. Geologic Conditions The shaft is at Merrittstown, which is about one mile northwest of Republic. The topography in the immediate vicinity of Merrittstown consists of rolling country dissected by the meanders of Dunlap Creek and its tributaries. The surface slopes of the hills are gentle and their average gradient is less than 6º. The area at the point where the study was made lies on a hillside sloping towards the southwest, the gradient, varying from 1º to 14º. Fig. 1 shows contour lines at 5-ft. intervals on

Jan 1, 1936

By Michel T. Halbouty

The area for which oil and gas development is reported for 1938 in this paper is larger than that covered by the report for 1937, in that besides Duval, Jim Hogg, McMullen, Starr, Webb and Zapata Counties, comprising the Laredo district, this paper also includes the South Corpus Christi district, which is composed of the following counties: San Patricio, Nueces, Jim Wells, Kleberg, Kenedy, Brooks, Willacy, Hidalgo and Cameron, all heretofore included in A.I.M.E. Gulf Coast reports. In the map, Fig. 1, the area known as South Texas is represented by the counties south of the heavy black line. Production in the South Corpus Christi district, which covers an area that extends inland for 50 miles and follows the coast line, is primarily in zones ranging from the Catahoula, through the Frio sands, into the Vicksburg horizon. General exploration is done mainly with geophysics because in this district production is directly dependent upon structural conditions. In the Laredo district most of the production is from sand lenses; therefore, because these shallow sand lenses represent old shore lines which are monoclinic in character, the most satisfactory method of exploration in the Laredo district is drilling. This type of production centers around Duval County and follows a northeast-southwest trend along the Mirando district. Although drilling operations showed a decline from the preceding year, 1938 was highly successful as far as new discoveries and developments were concerned, and results of the year's operations should have an important effect on the near future trend of exploration and drilling. Besides the discovery of several new fields and many new sands in established fields, 1938 saw the discovery of a new Vicksburg sand trend and the first marine drilling off the South Texas Gulf Coast. Many new fields were discovered during the year, but only a few were subjected to an extensive drilling program. Several already established fields, especially in the Laredo district, received a large amount of drilling as new sands and extensions enlarged the producing areas, a

Jan 1, 1939

By Charles S. Barrett

Recrystallization textures—thc orientations of grains after recrys-tallization—have been studied extensively not only because of their metallurgical importance but also because of the information they yield regarding the atomic movements during reerystallization. Recrystallized grains must possess the same orientations as the submicroscopic nuclei from which they have grown, and thus they offer a direet road by which experimenters can penetrate the submicroscopic realm. Many perplexing results have come of these studies, but one of the most striking has been the apparent difference in behavior between single crystals and polyerystalline grains. For example, Burgers and Louwerse have shown1 that when single crystals of aluminum are deformed by compression and are reerystallized (at 600' C.) the new grains appear with orientations that are different from the orientations of the deformed crystal in which they grew; but polycrystalline specimens, on the other hand, appear to have a [110] fiber texture both before and after reerystallization and thus to retain their texture during recrystallization. This apparent difference between the habits of single crystals and small grains is the subject of the first part of the present research and has been explained by findings reported herein. A similar situation appears to exist for aluminum when elongated or drawn into wires, for single crystals alter their orientation 2,3 and polycrystalline wires retain their texture"5*" upon recrystallization after elongation (at least with high-purity aluminum), and it is possible that the explanation found in this paper for compression can be extended to cover elongatioil and other types of deformation as well. The second part of this paper deals with the theory of reerystallization textures. In the most successful theory for aluminum reerystallized after compression,1 much weight is given to the orientation of highly stressed nuclei in the deformed material. Taylor's "local distortions" arc assumed to exist along the slip planes where displacement has occurred, consisting of fragments rotated in a specific way with reference to the slip plane and slip direction; namely, about an axis lying in the slip plane perpendicular to the slip direction.1,7,89

Jan 1, 1940

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,'' indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By Lennart Wellenius

LAISVALL - ONE OF THE BOLIDEN MINES Until the Aitik Mine (2,000,000 mtpy) started in 1968 the Laisvall Mine (1,200,000 mtpy) was the biggest unit of about 20 producing mines, belonging to the Boliden Company Ltd. As shown in Fig. 1 the mines are spread over a wide area. Most of them are small complex ore mines (50,000 - 300,000 mtpy), for which reason the total mine production does not exceed 5,500,000 mtpy. When our company was invited to present a paper, Laisvall was chosen because it is the biggest European galena-mine in production today. The Laisvall Mine is situated in the county of Norrbotten, Sweden, at the eastern border of the Caledonian mountain-chain. The road distance to Slagnäs, the nearest railway station, is 60 miles. The railway between Slagnäs and BOLIDEN's smelting plant, the Rönnskär Works, is 140 miles long. PRODUCTION STARTED IN 1943 In the Autumn of 1938 a boulder was discovered, consisting of sandstone with galena, on the shore of the Lake Stor-Laisan. The boulder came from an Eocambrian sandstone formation, which is overlain by Cambrian-Silurian rock.

Jan 1, 1970

By L. N. Plein, F. W. Newhall

During the latter part of the year 1931, the Republic mine of the Republic Steel Corporation, at Republic, about 4 miles south of Brownsville, Pa., was mining coal along four rib or fracture lines. One of these lines, the west butt rib line, was retreating towards a concrete-lined air shaft, 320 ft. deep, which had been sunk in 1911 for ventilation purposes. With the normal rate of mining at that time, it was expected that this rib line would pass the shaft in three or four months and the shaft would then be abandoned and allowed to cave. Realizing the opportunity presented for the study of an unusual case of ground movement, the question of conducting the study was presented by the junior author to thechairman of the Institute's committee on Ground Movement and Subsidence, Mr. George S. Rice, who presented the matter to Mr. G. H. Morse, General Manager of the Northern Mines, Republic Steel Corporation, and he agreed to cooperate with the Bureau of Mines in making the study, the results of which arc presented in this paper. Acknowledgments are due to Mr. Morse for his full cooperation in this work and to Mr. G. S. Rice and Mr. J. W. Paul, both of the U. S. Bureau of Mines, for their advice and guidance during the course of the work. The authors are indebted to Mr. B. F. Herbert, mining engineer, Northern Coal Mines, Republic Steel Corporation, who assisted in all the surveys, and Mr. W. H. Smith, draftsman, U. S. Bureau of Mines, who prepared all illustrations for publication. Geologic Conditions The shaft is at Merrittstown, which is about one mile northwest of Republic. The topography in the immediate vicinity of Merrittstown consists of rolling country dissected by the meanders of Dunlap Creek and its tributaries. The surface slopes of the hills are gentle and their average gradient is less than 6º. The area at the point where the study was made lies on a hillside sloping towards the southwest, the gradient, varying from 1º to 14º. Fig. 1 shows contour lines at 5-ft. intervals on

Jan 1, 1936

By H. C. Goodrich

At the Utah Copper mine, steam shovels were first used, in 1906, for the removal of overburden, and in June, 1907, for the mining of ore. Prior to 1907, the ore came from underground development work and from stoping. The use of the steam shovel gradually increased until 1914; since then all material, both overburden and ore, has been loaded by power shovels operating on the various benches of the mine. During these 19 years, there has been a great improvement in open-pit mining, largely in the use of equipment having greater capacity and dependability. The history of the development of mechanical shovels and related equipment, as affecting the Utah Copper Co., would be interesting and would justify considerable space; but of greater interest at this time is the operation of the equipment now in use. The Utah Copper mine is in a great deposit of copper-bearing monzo-nite, which occurs as a prominent headland of the Oquirrh range of

Jan 1, 1925

By H. M. Stewart, R. A. Grange

MANY steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering " and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully under- stood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually dl marten- site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered marten- site and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTEN- SITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1946

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By Michel T. Halbouty

The area for which oil and gas development is reported for 1938 in this paper is larger than that covered by the report for 1937, in that besides Duval, Jim Hogg, McMullen, Starr, Webb and Zapata Counties, comprising the Laredo district, this paper also includes the South Corpus Christi district, which is composed of the following counties: San Patricio, Nueces, Jim Wells, Kleberg, Kenedy, Brooks, Willacy, Hidalgo and Cameron, all heretofore included in A.I.M.E. Gulf Coast reports. In the map, Fig. 1, the area known as South Texas is represented by the counties south of the heavy black line. Production in the South Corpus Christi district, which covers an area that extends inland for 50 miles and follows the coast line, is primarily in zones ranging from the Catahoula, through the Frio sands, into the Vicksburg horizon. General exploration is done mainly with geophysics because in this district production is directly dependent upon structural conditions. In the Laredo district most of the production is from sand lenses; therefore, because these shallow sand lenses represent old shore lines which are monoclinic in character, the most satisfactory method of exploration in the Laredo district is drilling. This type of production centers around Duval County and follows a northeast-southwest trend along the Mirando district. Although drilling operations showed a decline from the preceding year, 1938 was highly successful as far as new discoveries and developments were concerned, and results of the year's operations should have an important effect on the near future trend of exploration and drilling. Besides the discovery of several new fields and many new sands in established fields, 1938 saw the discovery of a new Vicksburg sand trend and the first marine drilling off the South Texas Gulf Coast. Many new fields were discovered during the year, but only a few were subjected to an extensive drilling program. Several already established fields, especially in the Laredo district, received a large amount of drilling as new sands and extensions enlarged the producing areas, a

Jan 1, 1939

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By Harry C. Swanson

TRANSPORTING concrete from mixer to forms has always been a problem. Twenty-five years ago this task was generally accomplished by means of wheelbarrow or concrete buggy. On large dam jobs, as the number of these projects increased, the gantry crane or highline came into use. Today several methods of handling concrete are employed on smaller surface construction jobs, for example, transit-mix trucks or dumpcrete trucks, which have crawler cranes with buckets for placing concrete into forms. In 1944, during early stages of developing Mather mine A shaft, several large underground concrete jobs were necessary. At this time the Cleveland-Cliffs Iron Co, purchased the first pump-crete machine, introduced by the Chain Belt Co. of Milwaukee. The machine was used to pour approximately 200 cu yd of concrete for a dam, or bulkhead, located 400 ft from the shaft. Concrete was mixed on surface, lowered down the shaft 1000 ft in a 2-cu yd bucket hung under one skip, spouted into the bowl of the pumpcrete machine from the bucket, and pumped directly into the forms. Since the day of the first pipeline concrete in 1944 to the present time, other equipment and other methods have been developed to permit transportation of concrete by pipeline through vertical and horizontal distances totaling 1 mile from mixer to forms. Much of the efficiency in present handling of underground concrete can be credited to the Bethlehem Cornwall mines, where concrete was transported through 6-in. pipe for great distances down an inclined shaft and along levels into forms.&apos; During initial development of Mather mine B shaft, with concrete work under way on two or more levels at one time, the pneumatic concrete placer, Fig. 1, was selected as best adapted for underground concrete transportation. The 3/4-cu yd pneumatic placer is a small machine readily moved from one location in the mine to another. It can be equipped with two sets of mine car wheels, which will permit moving on regular mine tracks. It is therefore possible to send concrete through the pipe at great velocity; the pipeline is clean after each shot except for the film of cement adhering to the inside. With the proper slump in the concrete, it is possible to shoot concrete 2000 ft with this machine, using the mine supply of compressed air at 95 psi. This equipment was first used at Mather mine B shaft to concrete slusher drifts, Figs. 2 and 3, and finger raises located about 2000 ft from the shaft. In several instances there were bends into crosscuts and up vertical distances into the forms. For the first pours two placers were used. The first was located near the shaft where the concrete could be spouted into it from a 2-cu yd concrete bucket on the cage. The second was set on the side of the drift at a point approximately 1500 ft from the shaft. The concrete was shot directly into the second placer from the first unit and from the second machine directly into the forms. After completion of several pours with the two machines, a trial pour with only one placer located at the shaft proved that the second placer could be eliminated. Since then all pours have been successfully completed with only one placer underground. As production of iron ore from the mine increased and the development program expanded, use of the cage for handling mine supplies and concrete became a major problem. This brought about the first attempt at shooting concrete vertically down the shaft for 2600 ft. A 6-in. pipeline with victaulic couplings installed during shaft sinking was used for the trial. One placer was set on surface 250 ft from the collar of the shaft so concrete could be spouted directly into it from the mixer. This machine shot the concrete 250 ft horizontally on surface to the shaft, 2600 ft vertically down the shaft, and 100 ft horizontally into the second placer located near the rib of the shaft station or plat. The second machine shot the batch into the forms, about 2000 ft. Total distance horizontally and vertically was 4800 ft. The entire time cycle for a ¾-cu yd batch of concrete from the mixer on surface to the forms underground totaled about 5 min. During the past two years the two-placer method from the mixer on surface to the forms underground has proved a very efficient means of transporting underground concrete. Advantages of using pipeline concrete are as follows: 1—Interference with normal mining operation is eliminated. When the cage, skips, mine cars, or mine openings are used for transporting concrete and materials used for making concrete, mine operation suffers in one way or another.

Jan 1, 1955

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer&apos; and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By C. J. Bechtoldt, H. C. Vacher

Quenched alloys, prepared by powder metallurgical techniques, were examined by microscopic and X-ray diffraction methods. The compositions and heat treatments were chosen so that the chromium and nickel solvuses could be determined and a range of composition and temperature, in which a eutectoid had been reported, could be explored in small intervals. The results showed no evidence of eutectoid reactions having taken place. ALLOYS containing iron, chromium, molybdenum, and nickel are extensively used in high-temperature applications. In order to provide basic information on the solid-state reactions that occur in such alloys, the National Bureau of Standards is engaged in an extensive study of the equilibrium phases in the binary, ternary, and quaternary systems involving these four metals. Attention was directed to the chromium-nickel system because a review of the literature showed conflicting data. A recent compendium1 of the constitution of binary alloys gives two diagrams for the chromium-nickel system, one a simple eutectic and the second a diagram showing a eutectoid and a eutectic. The eutectoid was the result of an allotropic transformation in a high-temperature solid-solution form of a chromium-rich phase called 0. The approximate temperature and composition of the eutectoid was 1200°C and 30 at. pct Ni. In the preliminary study, at the Bureau, no transformation was indicated in the chromium-rich phase of ternary and quaternary alloys in which chromium and nickel were major components. Similar results have been reported from time to time in the literature,2-8 In consequence of this situation, a systematic study was made of the constitution of heat-treated chromium-nickel alloys using metallographic and X-ray diffraction methods. The compositions of the alloys were selected so as to determine the boundaries of the chromium-rich and the nickel-rich phases and to explore in small intervals the ranges in composition and temperature in which the eutectoid had been reported. The results of this study are reported and discussed in the present paper. EXPERIMENTAL PROCEDURES Materials, Alloys, and Heat Treatments—The alloys were prepared by a powder metallurgy technique similar to that used in earlier work.9 Analyses of the materials used are given in Table I. Powders were mixed using a vibrator in 30-g batches of predetermined composition; 2-g pellets were made from the mixture by compacting at room temperature in a 1/2-in. diam mold under 60,000 lb per sq in. pressure. The pellets were sintered in dry hydrogen for 10 days at 1300°C. At the end of the sintering treatment the specimens were quenched in water, which caused a pale green film to form on the chromium-rich alloys and thin black scale to form on the nickel-rich alloys. The pellets after sintering were approximately 1/2 in. diam by 3/32 in. thick. The purification train9 was modified by inserting a tube of titanium turnings, heated at 700°C to increase the efficiency of the removal of oxgen and nitrogen. It was found in the earlier work that the sintering treatment lowered the carbon, oxygen, and nitrogen contents of chromium-rich alloys to 0.01, 0.01, and 0.004 wt pct, respectively, and that there was a loss of chromium. In order to ascertain the extent of this loss, the chromium contents of certain alloys were determined chemically. They included those alloys used to determine the parameter-composition curves and those of critical composition, used to determine the chromium-solvus microscopically; these analyses were made on samples after the final heat treatments. The mixed powder values for the chromium content of those alloys that were not analyzed were adjusted to conform to a smooth curve based on the chemically analyzed values for

Jan 1, 1962

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965