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By A. D. Zunkel, A. H. Larson

Equilibrium antimony contents of pb-sb alloys in contact with PbO-Sb2O3 slags containing less than 45 mole pct Sb203 uleve determined at 650', 700°, and 750°C in an inert atmosphere. In this ten~pevature range, the antimony contmzt of the alloy increased with increasing temperature at all slag compositions. The PbO-Sb203 phase diagram below 28 mole pct Sb2O3 was determined by thermal analysis and by application of a log sbZ4/y$b0 us plot determined from the equilibrium-activity data. The resulting phase diagram showed a eutectic at a temperature of 604°C and a comfiosition of 21.6 mole pct Sb2O, with a maximum terminal solid solubility of Sb203 in PbO of 5.6 mole pct. These results are compared with existing data in the literature. In the past three decades, only a small amount of experimental work has been done on the slag-metal equilibria in the Pb-PbO-SbaO3 or the analogous arsenic and tin systems. These systems are important in commercial lead-refining processes such as softening and dross fuming since it is impurities such as antimony, arsenic, and tin in lead bullion and Sb2O3, As2O3, and SnOz in lead drosses which must be re-

Jan 1, 1968

By Francis P. Sinn

LOW prices have made 1938 a difficult year for the zinc industry of the world. Particularly in the United States, output had to be radically curtailed to bring production into line with consumption. Despite these unfavorable conditions, some additional plant construction is contemplated. In Jugoslavia, through co-operation with the Government, Trepca Mines is lo build a zinc plant to produce 10,000 metric tons annually, the plant to be ready for operation in July, 1941). Cerro de Pasco is proceeding with its plans for an electrolytic plant in Peru. A pilot plant, to be ready next summer, is under construction. In eastern Canada an electrolytic plant is planned in Quebec to treat concentrates from Yoranda and other mines but no defi-

Jan 1, 1939

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954

By J. C. Melrose

The contact angle is one of the boundary conditions for the differential equation specilying the configuration of fluid-fluid interfaces. Hence, applying knowledge concerning the wettability of a solid surface to problems of fluid distribution in porous solids, it is important to consider the complexity of the geometrical shapes of the individual, interconnected pores. As an approach to this problem, the ideal soil model introduced by soil physicists is discussed in detail. This model predicts that the pore structure of typical porous solids will lead to hysteresis effects in capillary pressure, even if a zero value of the contact angle is maintained. The model is generalized to situations in which the contact angle takes on values between zero and 40 degrees. For the imbibition branch of the capillary- pressure function, the model predicts a considerable departme ftom the usually assumed cos 0 relationship. In fact, according to the model, it is possible that a displaced wetting phase will not be able to reimbibe, even when the contact angle does not exhibit hysteresis. INTRODUCTION The subject of capillarity in porous media has long been of interest in many branches of engineering and applied science. The earlier investigators were those concerned with the physics of soils. 1-5 More recently, petroleum engineers and others dealing with the problems of petroleum production from reservoir rock have given much attention to the subject.6-10 Also, important additions to the literature of capillarity have been contributed from the field of chemical engineering.11-12 These attest to the wide range of industrial applications in which capillary phenomena play a role. The present paper is concerned with the role which wettability plays in capillary action in porous media. As is well known, capillary-rise (or capillary pressure) phenomena have frequently been interpreted with the aid of a model employing the concept of a cylindrical capillary tube. This approach has enjoyed a certain degree of success in correlating experimental results.13 The generalization of this model, however, to situations which involve varying wettability, has not been established and, in fact, is likely to be unsuccessful. In this paper another approach to this problem will be discussed. A considerable literature relating to this approach exists in the field of soil science, where it is referred to as the ideal soil model. Certain features of this model have also been discussed by Purcel114 in relation to variable wettability. The application of this model, however, to studying the role of wettability in capillary phenomena has not previously been attempted in detail. In the present paper, additional features of the model are introduced. These features are critical in determining the quantitative behavior of the model. GENERAL FEATURES OF CAPILLARY HYDROSTATICS BASIC PRINCIPLES When the interstices of a typical porous solid are occupied by two or more immiscible fluid phases, the fluids are microscopically commingled. Hence, fluid-fluid interfaces are found within a certain fraction of the pore openings. The fundamental equation of capillarity specifies the configuration of these fluid-fluid interfaces. This is known as the Laplace equation, when derived from mechanics, and as the Gibbs-Kelvin equation when derived thermodynamically.15 Given two fluid phases, a and ß, in hydrostatic equilibrium, the Laplace equation states that the respective fluid pressures in regions close to the interface are related by Here oaß is the surface or interfacial tension and rl and r2 are the principal radii of curvature of the surface or interface. The pressure difference, Pa-Pß, is the capillary pressure, PC. As Buff15 has shown, Eq. 1 states the condition for hydrostatic equilibrium within the two-phase confluent region, which is referred to as the interface. It thus can

Jan 1, 1966

By R. F. Hinds

A pressurizing system was designed and built to apply a radial pressure of 5.000 psi to rock samples. Samples of the Bradford, Weir and Kirkwood sandstones were subjected to radial pressures parallel and perpendicular to the bedding in the system and the changes in conductivity, porosity and permeability were deter-mined. Asymptotic decreases in conductivity, porosity and Klinkenberg permeability were observed over the 0- to 3,500-psi range. From these data, the increase of formation factor over the same range was calculated. The cementation exponent expressed in the Archie equation was found to increase with pressu,re. The rate of change varied from formation to formation. Only small differences were observed for samples taken parallel to the bedding as comnared to those taken perpendicular to it except for the Bradford sand. Above 3,500 psi the data are not good enough to tell if the properties continue to fall-off asymptotically or in a different manner. A possible explanation for the probable litnit of the asymptotic rate around 3,500 to 4,500 psi is that this represents the maximum pressure which the formations have unrdergone during their geological life as a result of burial. INTRODUCTION For many years measurements have been made in the laboratory of the properties of oil-bearing sandstones with little consideration being given to whether these properties had been changed when the samples were moved from their original position in the ground to the laboratory. Relatively little has been reported in the literature on the effect of pressure on the properties of sandstones. The changes in permeability for eight typical consolidated oil-bearing sandstone samples with overburden pressure (0- to 15,000-psi range) was presented by Fatt and Davis' in graphical form. In 1953 Fatt' also reported the relationship between porosity and overburden pressure for four typical consolidated oil-bearing sandstone samples (0- to 5,000-psi range). Fatt later described the changes of formation factor and porosity of 20 typical oil-bearing sandstone samples with overburden pressure changes (0- to 5,000-psi range) giving the values of the coefficients and exponents in the Archie' equation, and the more general Winsauer equation', where C, k and m are empirical constants, F is the formation factor, and + is the porosity. During the experiments of this investigation the core was contained in a neoprene rubber sleeve as shown in Fig. 1. It was held between two steel end members which were mounted in a steel cylinder. The unassembled pressure cylinder with its component parts is shown in Fig. 2. The core was insulated from the two steel end members by a Teflon sleeve with a small hole in the

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision's prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision's prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By L. R. Ingersoll, James Fisher, Harry Vivian

The copper mines of the Keweenaw Peninsula in northern Michigan have long been of interest in connection with deep earth-temperature measurements. The extraordinary low geothermal gradient of l° F. in 223.7 ft. announced by Agassiz1 as a result of measurements dating from 1886, although later2 stated as in error, served to focus attention on this region as one offering, because of the great depth of the mines, unusual opportunity along this line. Lane,3 Van Orstrand4 and others have made valuable contributions to this study. Fresh opportunities afforded by the constant deepening of the mines, improvements in the accuracy and reliability of temperature-measuring instruments together with increasing knowledge of the heat conductivities and specific heats of the rocks, led the Michigan College of Mining and Technology in cooperation with some of the mining companies to renew work on this problem. It is planned eventually to complete a survey which will make use of the favorable opportunities for deep rock-temperature measurements presented in these mines. This survey should include the determination of a depth-temperature gradient in both conglomerate and arnygdaloid mines, and also the variations in temperature at the same depth in different geological formations. The first problem has a direct bearing on the question of providing equipment for necessary ventilation with increased depth. The second may show that a relation exists between the natural rock temperature and the mineral content of the formation. The measurements in all cases are to be guided by heat conduction considerations, to the end that they may represent as closely as possible

Jan 1, 1934

By T. L. Joseph

THE invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.1 After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it. His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be encountered from oxidation of the iron. Mushet was not only an inventor but he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, arid he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 5, 1927

By J. E. Gould, H. J. Hand

MANY independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final deoxidation In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding over-deoxidation to minimize the amount of inclusions present and to make as sound a steel as possible For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or long FeO values The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishing the state of oxidation at a given time Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors Data obtained are from actual furnace operations, the metal test being of the spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States Steel Corporation This method of taking open-hearth metal temperature was invented by Collins and Oseland,1 and was developed into its present form by L 0 Sordahl,2 of the Research Laboratory The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications 3,4,5 Slag components were obtained by chemical analysis Data were taken from four 165-net-ton furnaces during the working period of the heat Recognizing that additions of ore affect the

Jan 1, 1942

By J. W. Taylor, E. G. Zukas

THE results of shock-loading studies on copper were reported several years ago by smith. In his experiments, Smith found that there was a correlation between the shock direction and the orientation of twins which the shock produced. By using free-surface-type shots in which the free surface of the specimen was not normal to the shock direction, he showed conclusively that twinning of copper in impulsive loading was caused by the rarefaction wave. Similar tests with iron, however, showed that it twinned during compression. More recent studies of iron2 and on Fe-Si single crystals3 have shown that twinning can be suppressed in these materials by shock loading at pressures high enough so that the velocity of the shock wave exceeds the elastic-wave velocity. From these observations, it appeared that twinning was caused by the shear stresses present in the zone undergoing adjustment from one-dimensional to three-dimensional loading. At high pressures, such a zone becomes so thin that there is insufficient time for the relatively ordered motion of atoms involved in twinning to occur. Twinning in copper, therefore, cannot be produced by a single compressive shock wave because resolved shear stress large enough to create twins exists only for a very short time (0.01 psec or less) before the pressure increases suddenly and loading becomes essentially hydrostatic. (A typical pressure vs time record for a copper shot, illustrating the short rise time of the compression wave, is shown in Fig. 1.) If, on the other hand, a second shock wave can be created in a precompressed sample, then the new elastic limit is several kilobars,4 and a resolved shear stress sufficient to cause twinning should be maintained for an adequate time period (0.1 psec or more). This experimental situation can, in fact, be realized. The experimental arrangement used to do so is shown in Fig. 2. By utilizing the pressure transformation in Fe-V alloys, it was possible to shock-load the copper in compression while the copper was already precompressed. In the first test, an 8 wt pct V-Fe sample was used as a driver for loading the copper, and the copper was exposed to the following series of compressive shocks: 1) an elastic wave of about 8 kbars, which is usually ignored in shock studies; 2) the pressure transformation wave for the driver of 200 kbars; and 3) the driving shock wave of 270 kbars pressure. Metallurgical determination of the angular twin distribution, shown in Fig. 3, with respect to the shock direction and the shock rarefaction direction (which was 23 deg from the shock direction) showed that twinning took place

Jan 1, 1965

By V. H. Wilhelm

The year 1941 in the California oil industry was marked by an increased market demand, drilling activity, and production of crude oil. Although seven new oil fields and two gas fields were discovered during the year, additions to reserves from these discoveries, as well as extensions and revaluations of previous discoveries, were approximately 100 million barrels, as against estimated withdrawals of 230,233,000 barrels. The year was remarkable for the very great increase in domestic demand for all products, which more than compensated for the loss in shipments to Japan, which averaged 60,041 bbl. Per day during 1940. Demand in terms of crude during 1941 was 648,967 bbl. per day as against 632,647 for the same period in 1940. This abnormal increase in demand is due to increased industrial activity, and especially increased railroad activity. Gasoline consumption for 1941 was 241,011 bbl. per day as against 217,744 in 1940. Demand for fuel oil increased from 259,806 bbl. per day in 1940 to 285,896 in 1941, and caused a withdrawal from stocks of more than 7,473,000 barrels. During 1941, total oil storage declined 9,153,000 bbl., but additions to storage of 1,754,000 bbl. of light oil and light oil products were offset by a withdrawal of 10,907,000 bbl. of heavier products. Production during the year is estimated at 230,233,000 bbl. as against 222,784,386 bbl. for 1940. TraNsportation For a short time, California was affected by lack of transportation due to the diversion of tankers. This shortage affected the movement of oil from the Sari Joaquin mated to the refineries, since a large percentage of this production is moved to the coast through pipe lines, and thence by tankers to Los Angeles and San Fran-,iSco, Return of the tanker fleet, which may be temporary, indicates that there is a possibility of ample supplies of petroleum products in the Pacific Northwest. Drilling Activity Contrary to general opinion, drilling activity increased in 1941 over the pre-vious Year, 942 wells being completed in 1941 as against 890 in 1940, an increase Of 6 per cent. This increase was due to the increased demands for fuel oil, and also to the decreased drilling costs, which made many former marginal locations economic. The main activity caused by increased demands for fuel oil was in the Mt. Poso, McKittrick, Midway and Santa Maria Valley oil fields. Dry-hole footage in 1941 was 655,354 ft. as against 583,537 ft. for 1940. Curtailment Voluntary curtailment succeeded in holding production considerably below demand, although it was above the state quota. During the year the top allotment

Jan 1, 1942

By V. H. Wilhelm

The year 1941 in the California oil industry was marked by an increased market demand, drilling activity, and production of crude oil. Although seven new oil fields and two gas fields were discovered during the year, additions to reserves from these discoveries, as well as extensions and revaluations of previous discoveries, were approximately 100 million barrels, as against estimated withdrawals of 230,233,000 barrels. The year was remarkable for the very great increase in domestic demand for all products, which more than compensated for the loss in shipments to Japan, which averaged 60,041 bbl. Per day during 1940. Demand in terms of crude during 1941 was 648,967 bbl. per day as against 632,647 for the same period in 1940. This abnormal increase in demand is due to increased industrial activity, and especially increased railroad activity. Gasoline consumption for 1941 was 241,011 bbl. per day as against 217,744 in 1940. Demand for fuel oil increased from 259,806 bbl. per day in 1940 to 285,896 in 1941, and caused a withdrawal from stocks of more than 7,473,000 barrels. During 1941, total oil storage declined 9,153,000 bbl., but additions to storage of 1,754,000 bbl. of light oil and light oil products were offset by a withdrawal of 10,907,000 bbl. of heavier products. Production during the year is estimated at 230,233,000 bbl. as against 222,784,386 bbl. for 1940. TraNsportation For a short time, California was affected by lack of transportation due to the diversion of tankers. This shortage affected the movement of oil from the Sari Joaquin mated to the refineries, since a large percentage of this production is moved to the coast through pipe lines, and thence by tankers to Los Angeles and San Fran-,iSco, Return of the tanker fleet, which may be temporary, indicates that there is a possibility of ample supplies of petroleum products in the Pacific Northwest. Drilling Activity Contrary to general opinion, drilling activity increased in 1941 over the pre-vious Year, 942 wells being completed in 1941 as against 890 in 1940, an increase Of 6 per cent. This increase was due to the increased demands for fuel oil, and also to the decreased drilling costs, which made many former marginal locations economic. The main activity caused by increased demands for fuel oil was in the Mt. Poso, McKittrick, Midway and Santa Maria Valley oil fields. Dry-hole footage in 1941 was 655,354 ft. as against 583,537 ft. for 1940. Curtailment Voluntary curtailment succeeded in holding production considerably below demand, although it was above the state quota. During the year the top allotment

Jan 1, 1942

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By H. E. McCoy, C. J. McHargue

Single crystals of columbium containing various levels of oxygen, nitrogen, carbon, or hydrogen were deformed by slaw compression and impact loading at -196°C. For the slow deformation rates. 1500 to 1900ppm oxygen, 500 pprn nitrogen, or 150 to 200 ppm carbon completely suppressed mechanical twinning. Hydrogen in concentrations to 1000 ppm had no apparent effect on ease of twinning. Impact loading caused twins to form at all levels of contamination studied, and cleavage mucking on (100) planes occurred in specimens having higher interstitial contents. It is well established that, under some conditions, the bcc metals vanadium, columbium, tantalum, chromium, molybdenum, tungsten, and iron deform by formation of mechanical twins. In general it has been accepted that high strain rates, low temperatures, and large grain sizes are conducive to this kind of deformation.' Since interstitial impurity atoms have a relatively large effect on slip in bcc metals, one might sus- pect a similar effect on twinning. This could occur directly by the interstitials affecting the nucleation or growth of the twins or indirectly from their effect on slip. It has often been argued that the large increase in yield stress caused by interstitial elements enables the effective stress to exceed that necessary to cause twinning. The twinning stress has always been thought to be higher than the stress necessary to cause slip in pure metals.2 simonsens and Tipper and Hall4 found profuse twinning in very pure a iron even at room temperature, whereas Low and Fueste15 and Churchman and tottrell' observed twins in a iron containing carbon but none in highly decarburized specimens. McHargue7 reported mechanical twins to form readily in vanadium which contained 390 ppm interstitigs, while Clough and Pavlovic8 found twins only in the one or two grains adjacent to the fracture surface in vanadium which contained 1500 to 1700 ppm interstitials. In columbium, McHargue9 found high-purity single crystals to twin easily whereas Churchman,10 Adams, Roberts, and mallman,11 and Johnson12 studied less pure material and found far fewer twins. Although the results of Leadbetter and Argent13 showed oxygen to inhibit twinning, a study by sheely14 indicated the opposite to be true. Chromium exhibits this mode of deformation15,16 but there are no data regarding impurity effects. Lawley, Van den Sype, and Maddin17 observed twins in very pure molybdenum single crystals deformed at 77°K but none in less pure crystals. The work by Cahn18 and

Jan 1, 1963

By E. C. W. Perryman

The recovery and recrystallization characteristics of superpurity aluminum have been investigated using electrical resistivity, X-ray line breadth, and hardness measurements for the former and the micrographic method for the latter. The three different properties recover at different rates and have different activation energies. The recrystallization results agree well with Avrami&apos;s theory and furthermore indicate that the perfect subgrains formed during recovery are not the nuclei for re-crystallization. WHEN a metal is plastically deformed, its physical and mechanical properties generally undergo considerable changes and by subsequent annealing these changes are partly or wholly annihilated. Thus, a recovery process can be discussed, taking this term in its general sense. In practice, however, there is reason to discriminate between two apparently different processes, one most easily followed at low temperatures, in which the properties return to an almost constant value between that of the cold worked and fully annealed material, and a second process in which the properties return to their original values before cold working and which is accompanied by the formation and growth of new grains having an orientation different from that of the matrix. In this paper the word recovery will be taken to mean the changes in some property as a function of annealing time which occur either without the appearance of new grains or under conditions such that the new re-crystallized grains are very small (= 2 microns), are very few in number, and substantially do not affect the property being measured. This definition is rather abitrary, for it will depend upon the sensitivity of the technique used for the observation of new recrystallized grains, which in the present work was about 1 to 2 microns. However, it is helpful to use the term recovery in this sense and to reserve the term recrystallization for the processes of nucle-ation and growth of new grains in the cold worked matrix. Although considerable work has been done on recovery and recrystallization, most workers have based their study on the measurement of one or perhaps two parameters. Since very small amounts of impurities have such a profound effect on the recrystallization characteristics of a pure metal, it becomes extremely difficult to correlate one piece of work with another. With this in mind, the present work on recovery and recrystallization was done on the same material. Experimental Procedure Material Used and Fabrication: The composition of the superpurity aluminum used throughout this investigation was 0.002 pct Cu, 0.003 pct Fe, 0.003 pct Si, and <0.001 pct Mg. The ingot was hot rolled to 0.250 in., annealed, and cold rolled to 0.034 in. A large number of reductions and intermediate anneals were carried out so as to produce material with a minimum of preferred orientation and maximum homogeneity. For the recovery part of the investigation, the final cold reduction was 20 and 80 pct and for the recrystallization part, 20 pct. After each pass in the cold rolling process, the material was quenched in cold water in order to keep the rolling temperature as near room temperature as possible. Annealing Procedure: For the recrystallization work, specimens 1x1 in. were cut from the 0.034 in. cold rolled sheet and a hole was drilled in each through which a wire was threaded to support it in the salt bath. The temperature of the salt bath was controlled to +2°C and the time taken for a specimen to reach temperature was approximately 5 sec. These 1 in. squares were then divided into three groups, one of which was given 5 min at 318°C and another 2 hr at 244°C. These treatments were such that recovery was almost complete and a well defined subgrain structure produced. Separate specimens of each group were annealed for different times at 301°, 318°, 355°, and 373°C, i.e., three specimens for each annealing time. The delay between finish of cold working and start of annealing was about 1 hr. For the recovery work, strips 0.062 in. thick were cut from the cold worked sheet, annealed, and then given the last cold rolling operation. This was done for each annealing temperature. By this means it was possible to minimize the delay between cold working and annealing. In general, all measurements were carried out within 1 hr of the last cold rolling operation. Annealing at low temperatures was done in an oil bath the temperature of which was maintained constant to +1°C. Electrical Resistivity Measurements: Strips 20x0.5x0.05 in. were machined and the electrical resistance measured using a Kelvin double bridge. Measurements were made in an oil bath maintained at 20rt0.1°C. The same specimen was used for the complete isothermal annealing curve.

Jan 1, 1956

By R. H. Johnson

All strata not yielding oil or gas in commereial quantities or a corresponding amount of water may be called dry in a wide sense. In petroleum geology, however, we may exclude all sands of too low or fine porosity to yield gaseous or fluid contents to the hole drilled in the sand before any original pressure that its contents may be under is disturbed. Most rocks are of this class and they are not reservoirs in our definition; their "dryness" is wholly a matter of course. What are the contents of the pores or what is the exact porosity of such rocks is of almost no concern to us, for economically they are "dry." What does interest us is the content of a rock having sufficient porosity and the pores of sufficient size to yield oil or gas in commercial quantities, if they were present under original pressure. Dryness of these reservoirs is a matter of supreme practical importance. Three views current as to such dryness seem, to me, to apply in a few cases only. It is the purpose of this paper to give reasons for this position and for believing that, in ordinary sedimentary rocks, there is only rarely a reservoir of competent porosity and undisturbed pressure that is dry in the sense of not yielding water, oil, or gas when first penetrated. 1. Gardnerl writes of some Kentucky sands, "There has never been present any salt water or other water in the sand." Absence of water cannot demonstrate this position. It is necessary to show that the rocks were not laid down in water, but in air, and that they became so enclosed, while still above the water-table of the ground water, that water has not been able to enter since. Most of these sands, and certainly the productive limestones, were deposited in water; and such sands as have been commercially productive show no reason for believing that the overlying shale or limestone was not laid down progressively from one direction and in water that would have flooded it. NO adequate explanation has been offered for this hypothesis, which is so inherently improbable. 2, Reeves2 urges that "sands originally water filled may have been drained of their water and not filled when later covered." It is difficult I James H. Gardner: Kentucky as an Oil State. Science, N. S. (1917) 46, 279-280. Reeves: Origin of the Natural Brines of Oil Fields. Johns Hopkins Univ. Circ., N. S. (1917) N. 3; Absence of Water in Certain Sandstones of the Appalachian Field. Econ. Geol. (1917) la, 354-378.

Jan 1, 1921