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By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.' EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2'3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

By Robert Sisselman

Dramatic changes have been effected since 1955 in the mode of iron ore shipments within the U.S. In 1955, less than one percent of ore consumed in domestic blast furnaces-approximately 125 million long tons-consisted of pellets. Five years later, in 1960, some 94.8 million tons of ore were consumed, 14% in the form of pellets. Projections for 1980 reinforce confidence in this most economic of blast furnace feeds, and set U.S. pellet consumption at 151.2 million tons. In the last decade, pellets caught fire in other countries. By 1969, world production reached 96 million tons. This compares strikingly with present world output of 154 million tons.

Jan 9, 1973

By Ernest F. Burchard

Fluorspar is found in most of the states from the Rocky Mountains westward, and commercial production of the mineral has been reported from Arizona, Colorado, Nevada, New Mexico, Utah and Washington. The map in Fig. 1 indicates the general distribution of many of these deposits but it is by no means complete. In the summer of 1926 the writer examined certain deposits of fluorspar in Arizona, California, Colorado, New Mexico and Washington; in November, 1927, revisited the Jamestown, Colo., district, and in earlier years examined deposits in Colorado and New Mexico. Based on notes of his own and on descriptions and other data by H. A. Aurand, H. W. Davis, R. B. Ladoo, V. C. Heikes, W. D. Johnston, Jr., and by producers of fluorspar, he prepared the following brief descriptions of deposits and estimates of reserves of fluorspar, originally for the use of the subcommittee on fluorspar of the Joint Committee on Foreign and Domestic Mining Policy and on Industrial Preparedness respectively of the Mining and Metallurgical Society of America and the American Institute of Mining and Metallurgical Engineers. Descriptions of many fluorspar deposits in various western states and districts have been published. It is not feasible to summarize this literature here, but the appended bibliography will indicate to the interested reader what papers are available. Arizona Fluorspar has been reported as occurring in Arizona in the following localities: near Duncan, Greenlee County; near Naco, Tombstone, and Paradise, Cochise County; Black Mountain, Mojave County; 25 miles southwest of Tucson, and at Helvetia and Silver Bell, Pima County; near Mammoth mine, Pinal County; in Yavapai County, 7 miles from Aguila, and in the Bradshaw Mountains; and near Dome, Yuma County. Production has come principally from the Castle Dome district, Yuma County, with minor quantities from Greenlee, Pima and Yavapai counties. The writer examined deposits in the Castle Dome district, Yuma

Jan 1, 1934

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While' it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind maybe said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others. In a generic way, metallurgists now speak of carbides, sub-carbides, double carbides, special carbides, and other combinations. It is very desirable that these should be accurately defined and understood. It is also desirable to know whether there are other or new forms; if so, can these be separated and their characteristics obtained. It may be interesting to point out that the carbon compounds now definitely known are stated to number over 80,000. It is very probable, therefore, that there is room for much valuable and useful research to be carried out with the object of increasing our knowledge of the various combinations of carbon with iron, as probably some of these are still unknown

Jan 5, 1914

By R. L. Dietrich

[ ] We at The Dow Chemical Co. have recently done some work on the deformation of magnesium alloys and although it is far from complete there have been a few observations which may be of interest in connection with this paper. In the first place, I should like to point out that the deformation of polycrystalline magnesium alloys has not been completely explained by the work on single crystals. Bakarian and Mathewson found slip on the ( 101) and {002) planes, and (102) twinning as the deformation mechanisms in magnesium single crystals, but in compression when the (002} planes were within ii° of parallel t0 the compression surfaces, fracture occurred at all temperatures up to 340°C (644°F). In commercial working processes, particularly in rolling, an orientation is quickly produced which should be unfavorable to further deformation by the three established mechanisms. The first few reductions in rolling quickly produce an orientation having

Jan 1, 1947

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state's annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company'sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan's No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state's annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company'sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan's No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By D. V. Carter, Dan C. Williams, John R. Coombs

Exploration was active in East and East Central Texas during 1944. Ten oil fields were discovered during the year, of which four show promise of development. The discovery wells of the Sand Flat and Tyler, South fields were drilled to a depth greater than 10,000 ft., and the latter field now produces from the Pettit at a depth of 9890 ft. The Sand Flat well was plugged back to the Paluxy. The other two fields are Glen Rose producers near 8000 ft. The Pickton field produces from the Bacon Lime and Winnsboro from the Rodessa section. The Eylau field, Bowie County, was significant as the first Smackover production in Texas. Magnolia drilled a test in the Concord field, which topped salt. The most extensive and significant development in the district was the Carthage gas-condensate field. It expanded from the 8000 acres of last year to an estimated 190,000 acres, or about 300 sq. miles, and is not defined as yet. The first oil production in the Carthage area was made from the Travis Peak in 1944 in the Rogers Lacy's Cameron Lumber Company well No. I, on the northwestern side of the field. The New Hope field, Franklin County, scored the largest number of completions during 1944 with 24, bringing its total number of wells to 27. Two more pays were opened and produced as dual completions with the older horizons. The Manziel field, Wood County, had 19 new wells added during the year, for a total of 29, while the Pittsburgh field, Camp County, reached a total of 23 wells by completing 14 new ones. Material shortages and drilling restrictions dropped the total number of producing wells completed in the district from 171 during 1943 to 141 for 1944. Abandonments increased from 531 during 1943 to 609 for 1944. Of this number, 479 were in the East Texas field. Subsidy payments had very little effect in the district and it was mostly a few of the old fault-line fields that had any wells to fall within the requirements for subsidy payments. The prices of crude oil remained constant in the district except for increases as a result of subsidy payments. Production and Probation Wartime demands called for increased allowables for many fields, consequently the condensate and oil production for 1944 increased to 190,016,180, which is up 6.9 per cent over 1943. The East Texas field, of course, remained the principal producer of the district, accounting for 134,768'499 bbl. during the year, or 71 per cent of the district total production of condensate and oil. The field topped its own 1943 production by 4.8 per cent and became the first field in the world to produce 2 billion barrels of oil. The Hawkins field remained the second largest oil producer in the district, with 13,317,088 bbl. for the year, a drop of 6.8 per cent from 1943, while Van field was third with 11,635,708 bbl. The

Jan 1, 1945

By Orlando E. Romig

As metals and alloys are composed of an aggregate of allotriomorphic crystals or grains, each possessing an individual orientation, the physical characteristics of a metal or an alloy are closely related to the properties of the individual crystals. The preparation and study of single metallic crystals are, therefore, matters of considerable importance. The advent of the X-ray spectrograph as a valuable metallurgical tool has magnified the importance of this subject, because the interpretation of some X-ray spectrographs is difficult unless single crystals are used in these studies. Previous Work The first paper, as far as the writer knows, on the behavior or preparation of single crystals of metals is by Baker.' He describes the behavior of extruded wires of sodium and potassium. These wires, when pulled in tension, instead of showing the usual conical fracture common to most metals, had a chisel-shaped fracture when they were broken. I and 11, Fig. 1, have a similar fracture. Baker checked his results by preparing single crystal wires from molten sodium and potassium and observing their properties. He pre- pared the wires by filling glass tubes, under oil, with the molten metal. The surfaces of the strained wires showed slip bands of remarkable clearness of which photographs are shown in his paper. He concluded that these wires were single crystals and "that the portions of the metal brought into play are cubes. Such cubes, when placed so that a plane through two opposite edges was parallel to the axis of the wire, would allow of lateral contraction by faces gliding over one another in one direction only and not in the direction at right angles."

Jan 1, 1927

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone', the giant Kirkuk field in Iran', the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn' observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,' Houska and Averbach,' and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.' cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.' Finally, the possibility of stress-induced order at dislocations, schoeck locking,' must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-' mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By R. M. Larsen

The Rocky Mountain region is defined with some variations for different purposes or by different organizations. For oil and gas development, Wyoming, Montana, Colorado, northwestern New Mexico, and Utah are included in the order of their apparent importance. Portions of adjoining states, such as North and South Dakota, Nebraska, Arizona, Nevada, and Idaho, arc attributary to this region, but have little or no oil or gas production. Nebraska and New Mexico are considered separately (see pp. 412 and 415), and most of the discussion in this report will be confined to Colorado, Montana, and Wyoming. Utah has produced about 200,000 bbl. of oil from the San Juan and Virgin fields, which are isolated and shut in at present. The Clay Basin field in northeastern Utah produces natural gas and distillate, and the Farnham field in central Utah produces carbon dioxide gas. Other Utah areas of some interest are listed in Table I. The Cedar Creek (Baker-Glendive) field in southeastern Montana extends into North Dakota, but is listed under Montana. The other states are in the main wildcat areas, and exploration in 1944 was at a minimum. However, geological and geophysical parties are reviewing them for further testing. Oil production in Colorado, Montana and Wyoming was 459,000 bbl. more than in 1943. Increases of 713,000 bbl. in Colarado and 731,000 bbl. in Montana offset a loss of 985,000 bbl. in Wyoming. This was the first decline in Wyoming since 1938. Field production figures and state totals are given in Table I. Total drilling activities in these three states and Utah increased from 687 wells making 1,442,511 ft. of hole in 1943 to 916 wells making 2,245,803 it. in 1944. Wildcat drilling increased from 163 wells making 331,193 ft. of hole in 1943 to 171 wells making 389,144 it. in 1944. These figures include all drilling wells making footage, not starts or completions, and represent an all-time high in drilling. The year 1944 witnessed the greatest concentration of seismograph activity that the region has had. The Rocky Mountain Oil Scouts Association reported that in 1943, the previous peak year, 91 crew months of work were performed; in 1944, the time was 254 crew months. About 67 per cent of the work was in Wyoming, 18 per cent in Montana, and 12 per cent in Colorado. Twenty-three blocks totaling 400,000 acres were reported assembled in Colorado, and 161 blocks totaling 4,000,000 acres in Wyoming. Information about other states was not given. Fourteen unit agreements were approved by the Department of the Interior, as compared with 13 in 1943. The 1944 agreements were all in Wyoming. In five of the unit areas, oil or gas discoveries were made, four were dry, and five were drilling Or pending' Oil companies find it advantageous to unitize blocks containing any proportion of public domain. Units for

Jan 1, 1945

By E. W. Pehrson, J. W. Furness

THE method of presentation in the accompanying charts is based upon the well-known formula: production plus imports minus exports equals apparent consumption. Thus for each area for which data are shown there are two columns of equal height, one representing production plus imports, the other apparent consumption plus exports. Usually no account has been taken of increases or decreases in stocks. All columns and flow lines are drawn to a linear scale which is supplemented by figures showing the actual quantities represented. Owing to the small area occupied by the European countries on the world map it was impossible to show the details of the trade of the individual countries. All of Europe (except Russia), therefore, is shown as a single unit. However, statistics of production and consumption indicated elsewhere on the charts show the degree of self-sufficiency enjoyed by the major European powers.

Jan 1, 1936

By Gail F. Moulton

The production of petroleum in Illinois in 1928 was approximately 6,500,000 bbl., a decline of about 500,000 bbl. from the previous year and of about 1,500,000 bbl. from 1924. Production increased about 200,000 bbl. in Indiana to slightly less than 1,000,000 bbl. Production for 1929 is estimated at approximately 6,000,000 bbl. for Illinois and 1,000,000 bbl. for Indiana. Illinois Because production from most of the wells in the state has declined to a small daily average and the low prices for crude oil discouraged wildcatting, the number of wells drilled fell below that for any previous year since the development of commercially important production in the state. The Ohio Oil Co. discovered a pool of apparent commercial importance in southwestern Illinois near Dupo, in St. Clair County, and favorable showings of oil were encountered in a well in southeastern Illinois, near Harrisburg in Saline County. New production from the Dupo area is expected to check the rate of decline for the state. Thc following tablel summarizes field developments for 1927 and 1928 (for important detail by counties see notes at foot of table): 1027 1928 Completions........................................... 162 145a Initial production, bbl.................................. 2244 1840b Dry holes........................................,.... 66 58" Gas well completions................................... 13 8d 0111 wells abandoned.................................... 45" a Crawford, 44; Lawrence, 28; Wabash, 40. b Crawford, 501; Lawrence, 403; St. Clair, 165 (4 completions); Wahash, 668. o Crawford, 12; Wabash, 19. d Crawford, 6. b Lawrence, 21; Wabash, 15. The discovery well in the Dupo field in St. Clair County, produced about 150 bbl. per day from the Trenton lime at 660 ft. It is located in a northern extension of the Columbia-Waterloo anticline on which the Waterloo pool was developed in 1921. The best information on the.

Jan 1, 1929

By C. Cronquist

Since April, 1962, Shell Oil Co. has operated a peripheral line-drive waterflood of the 10.750-ft lower Tuscaloosa (Cretaceous) Denkman sand in the Little Creek field. Located in southwestern Mississippi in the lower Tuscaloosa trend, the field was discovered by Shell in Jan., 1958. Among the largest in the trend, the accumulation is controlled stratigraphically and occurs in an extensive series of alluvial-point bar deposits across a nose that dips gently to the south. The crude oil is 39" API gravity and was highly undersaturated at initial conditions. Early production behavior indicated a depletion drive with slight water influx; primary recovery wm estimated to be 25 million bbl, or 24.5 percent of stock-tank oil originally in place. A.s a result of a favorable mobility ratio and remarkably uniform rock properties, the volumetric sweep eficiency in the waterflood has exceeded 90 percent. Despite the high connate water saturation (56 percent), the displacement efficiency by water injection has been quite efficient, contrary to traditional concepts. Based on observed field flood-out performance, ultimate recovery is calculated to be 46 million bbl. As anticipated, the production rate began declining during 1964 due to a continu ing reducrion in the number of producing wells as flood fronts advanced across the field. Cumulative recovery as of Jan., 1968, was 44.8 million bbl; waterflood operations ~hould be complete by 1970. Introduction Most waterfloods described in reservoir engineering literature involve pattern operations, the most common of which is the five-spot pattern. Only occasiona'lly are linear drives described, even though there probably are increasing numbers being put into operation. Increasing use of linear floods may reflect the accelerating trend towards early application of fluid-injection programs when linear drives are more efficient, as was the case at Little Creek. However. the Little Creek operation is unusual in several respects. It is one of a few successful waterfloods conducted in sands with connate water saturations approaching 60 percent, and it is among the deepest successful water-floods being operated anywhere. Development The Little Creek field was discovered in Jan., 1958, in the lower Tuscaloosa trend in southwestern Mississippi (Fig. 1). The discovery well, Shell-Lemann No. 1, was drilled on a seismic closure about 2 miles southeast of lower Tuscaloosa production at Sweetwater. The well was completed in the Denkman sand at 10,752 ft, and on initial potential it flowed 588 BOPD of 39" API crude on a %+-in. choke; psi was 730 and GOR was 442:l. Development proceeded rapidly on 40-acre spacing, and by the end of 1958 the field was producing approximately 9,100 B/D from 56 wells. Almost all this production came from the northern half of the field. The southern part was discovered in Nov., 1958, at a location almost 2 miles from previously established production. Subsequent drilling established an apparent conneotion about half a mile wide between the twd areas. Development of the field was practically complete by 1961 with the drilling of 155 producers and 35 dry holes. Some early wells were completed open hole but moslt are completed with casing cemented through the productive interval and perforated for production. Geology The lower Tuscaloosa structure in this area is a north-south nose with maximum dips of about 2" on the flanks. There is no discernible faulting at the producing horizon. Productive limits of the field are shown in Fig. 2, which is contoured on a marker just above the main productive zone. A common water level at 10,415 ft subsea was logged at both the northwest and southeast ends of the field. There is a gross oil column of nearly 100 ft (Fig. 2). Since there is less than 40 ft of closure, it is apparent that bhe accumubtion is controlled stratigraphically, being limited by a sand pinch-out across the creslt of the nose. The total produc-

Jan 1, 1969

By Louis D. Huntoon

After the completion, in 1905, of the Hammond Mining and Metallurgical Laboratory of the Sheffield Scientific School, Yale University, it became necessary to secure and assay a large assortment of ore-samples, and to arrange the results in such a manner as to admit of use with the least amount of work on the part of the instructor. At first, pulp-samples, together with their respective assays, were secured from the mines, smelters, and public aesayers, but this practice did not prove satisfactory. It was not only difficult to secure a suffciently large supply of material, but it was also impossible to secure the proper assortment required for instructing students. It involved considerable work for the donors to select the samples and furnish a record of the assays, and also for the instructors to examine each pulp and determine its character. Some of the samples did not contain a sufficient quantity of pulp for the student to check his work in case his first assay did not correspond to the record. In order to increase the number of samples and to vary the character of the material, pulp-samples were later mixed with barren rock and with sulphides, but this method also was unsatisfactory and has been discontinued. At present, small lots of ore are secured by gift or purchase from engineers, public assayers, and the managers of mines, mills, and smelters. These lots weigh from 10 to 100 lb. each, and are rarely finer than 0.25 in. in size. The larger samples permit of a careful study by the instructor in order to determine the best method of assaying to be followed. In universities in which assaying is taught the record of the samples should fulfill the following requirements:

Jan 1, 1910

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

THE CHAIRMAN (A. F. Lucas, Washington, D. C.).-Mr. Matteson has stated that the drilling of certain deep wells has proved a failure because they were abandoned too soon. He advises drilling more wells around salt domes, in the hope of finding additional oil sands. I have had some experience on the domes and believe that by drilling shallow wells, one loses time and money. I have advanced the opinion -that by drilling central wells in the -most likely location of a dome, showing is certain weakness, a better result could be obtained. I have in mind one locality where Mr. Knapp drilled a well through the salt¬the only location that I know of on the Gulf Coast where oil was found underneath the salt. Mr. Knapp found a great deal of gas in it. The salt itself was impregnated with oil and gas; and my opinion is that in such instances, instead of drilling so many wells around a dome, if you will attack at a weak point to as great a depth as a drill will go, the results will he much better. At present we have instances where drills have penetrated to 7300 or 7400 ft. in depth. Why couldn't the rich companies that are operating around the Gulf Coast arrange to get some special drilling apparatus and drill with the rotary first for, say, 3000 to 4000 ft., always in the likely location, and then proceed with the cable? I think we need just such work. In Mr. Matteson's paper lie quotes from an author whose writings in the Federal Bulletin and in the Louisiana Bulletins have been quite extensive. He states that oil and asphalt have originally been found on the surface of those domes. I have been over and examined nearly all of those domes (not all of them, because many have been developed in the last few years) and found no such occurrence at the time; and in the old well-known humps or big hills, as they generally called them; I have never found either salines or asphalt or petroleum. In only' one instance it looked as though asphalt night have exuded out of the ground, and that was in the Sour Lake, but right in that neighborhood years previous to that a company had operated commercially-they had a little refinery there-and had found it so unprofitable that they pulled up stakes and quit.

Jan 4, 1918