Search Documents

By M. King Hubbert, David G. Willis

A theoretical examination of the fracturing of rocks by means of pressure applied in boreholes leads to the conclusion that, regardless of whether the fracturing fluid be of the penetrating or non-penetrating type, the fractures produced should be approximately perpendicular to the axis of least stress. The general state of stress underground is that in which the three principal stresses are unequal. For tectonically relaxed areas characterized by normal faulting, the least stress should be horizontal; the fractures produced should be vertical with the injection pressure less than that of the overburden. In areas of active tectonic compression, the least stress should be vertical and equal to the pressure of the overburden; the fractures should be horizontal with injection pressures equal to or greater than the pressure of the overburden. Horizontal fractures cannot be produced by hydraulic pressures less than the total pressure of the overburden. These conclusions are compatible with field experience in fracturing and with the results of laboratory experimentation. INTRODUCTION The hydraulic-fracturing technique of well stimulation is one of the major developments in petroleum engineering of the last decade. The technique was introduced to the petroleum industry in a paper by J. B. Clark,' of the Stanolind Oil and Gas Co. in 1948, and since then its use has progressively expanded so that by the end of 1955 more than 100,000 individual treatments had been performed. The technique itself is mechanically related to three other phenomena concerning which ah extensive literature had previously developed. These are: (1) pressure parting in water injection wells in secondary-recovery operations, (2) lost circulation during drilling, and (3) the breakdown of formations during squeeze-cementing operations, all of which appear to involve the formation of open fractures by pressure applied in a wellbore. The most popular interpretation of this mechanism has been that the pressure had parted the formation along a bedding plane and lifted the overburden, notwithstanding the fact that in the great majority of cases where pressures were known they were significantly less than those due to the total weight of the overburden as determined from its density. Prior to 1948, this prevalent opinion had already been queried by Dickey and Andresen,2 in a study of pressure parting; and by Walker,"' who, in studies of squeeze cementing, pointed out that the pressures required were mostly less than those of the overburden, and inferred that the fractures should be vertical. J. B. Clark,' in his paper introducing hydraulic fracturing, and later Howard and Fast," and Scott, Bearden, and Howard," also of Stanolind, postulated that the entire weight of the overburden need not be lifted in producing horizontal fractures, but that it was only necessary to- lift an "effective overburden," requiring a correspondingly lower pressure. Hubbert,7 in discussing the paper by Scott and associates, pointed out that the normal state of stress underground is one of unequal principal stresses; and in tectonically relaxed areas, characterized by normal faults, the least stress should be horizontal. Therefore, in most cases, fracturing should be possible with pressure less than that of the overburden and, moreover, such fractures should be vertical. Harrison, Kieschnick, and McGuire,8 also on the expectation that the least principal stress should be horizontal, argued strongly in favor of vertical fracturing. Scott, Bearden, and Howard6 observed that, when

Jan 1, 1958

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,' in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.' Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.' The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By Walter Mathesius

The use of high blast heats on furnaces melting Mesaba ores is still the exception, the average blast temperatures carried on Mesaba stacks seldom reaching 1,100" F. Some 15 years ago, when the use of fine Mesaba ores in larger proportions to the total burden first came into practice, it was found difficult to employ even those blast heats which it had been possible ' to carry with the Old Range ores. The furnaces refused to "take" high heats, and would persistently labor with irregular stock movement, which impaired the practice and increased the coke consumption. By lowering the blast temperature, the working of the furnace became smoother, and experience taught that with the softer and more easily reduced Mesaba ores, satisfactory practice could be obtained with comparatively low blast heats. Therefore a large number of Mesaba furnaces have ever since been operated on very low blast temperatures, ranging between 800" and 1,000" F. In the face of these difficulties, furnace men were slow to recognize that furnaces could be so designed as to permit a free movement of the charges in combination with the use of higher heats. Since higher blast temperatures did not seem to offer great advantages in the smelting of Mesaba ores, investments in hot-blast stoves were not as attractive to the furnace man as labor-saving devices and means of obtaining greater tonnages. The effect of this preference is keenly felt at the present time. It has brought about the peculiar situation, that the majority of our furnace plants (among them some of the most progressive) lack modern and efficient stove equipment. The result is that, even where the proper furnace lines have been adopted and conditions are now favorable to the successful employment of higher blast temperatures, the heats required for the greatest fuel economy are not available. In an endeavor to obtain results, even with inadequate equipment, we find that, at many plants, the stoves are worked far beyond their capacity. This leads, in many instances, to a situation in which the coke saving in the

Jan 1, 1915

CARACAS PETROLEUM Established February 24, 1957 Official year begins in January Harry J Sykes, Chairman G J Clarke, Vice-Chairman Robert S Longwell, Vice-Chairman David L Stepanek, Treasurer Robert C Newman, Secretary Texas Petroleum Co Apartado 267 Caracas, Venezuela

Jan 1, 1960

By B. H. Caudle, L. G. Davies, I. H. Silberberg

This paper presents a method of predicting the recovery and performance of a five-spot steam injection project, in which a realistic approach to pattern sweepout efficiencies is made. Published methods for radial systems were modified for the five-spot pattern by approximating the stream lines with straight lines radiating from the injection well and then converging to the producing well. In each radial segment, the position of the steam front and the temperature profile ahead of the steam front were determined by heat balance equations, which included an estimation of heat losses to surrounding formations. The location of the saturations behind the cold water front was determined from a Buckley-Leverett solution to the material balance equation. Results from this program show steamflood recovery in a five-spot pattern to be considerably less than that predicted for true linear or radial flow systems. For a specific reservoir containing 900-cp oil, a steamflood in a purely radial flow system was predicted to recover more than 75 percent of the original oil in place when 2 PV of water had been injected as steam. A five-spot steamflood with otherwise identical properties was predicted to recover 10 percent of the original oil in place when 0.15 PV of water had been injected as steam and to recover almost no oil thereafter. A cold water five-spot flood in this system was predicted to recover approximately W percent of the oil in place with I PV of water injected. For a five-spot pattern in an example reservoir with 10-cp oil, steam injection similarly showed lower ultimate recovery than water injection but no improvement in recovery rule. Introduction The thermal recovery method considered in this study is steam injection in a five-spot pattern. Pattern steam injection has been given little attention in the past, possibly because of some rather obvious disadvantages. Unless steam temperature is maintained throughout the entire swept area, the process will revert to simple waterflood with all heat being lost prior to reaching the oil bank. Also, the oil viscosity reduction takes place near the steam front and not around the producing wellbore, so that low producing rates must still be endured. This is the reason for the success of the steam stimulation, or cyclic injection, in which the fluids are produced from the same well used for injection. On the other hand, steamflooding can offer some advantages. Oil displacement is by four methods: (1) mechanical displacement by the condensed water, (2) viscosity reduction of the crude oil, (3) swelling of the crude oil, and (4) distillation of the crude oil in the steam zone. Although dependent upon the crude, laboratory experiments have shown displacements up to 80 percent by steamflooding. In addition, steam is a good heat transport medium, since it is cheap and has a high heat content. Previous Investigations Previous publications have reported methods for predicting recovery in a steamflood for linear and radial systems. Since no pattern sweep efficiency is taken into consideration, the recovery even from a radial system must be greater than from more realistic geometries such as the very common five-spot patterns. Probably the broadest coverage is given by Willman who reported experimental results and offered a method of predicting recovery for a radial flow system. They concluded that both hot water and steam injection recover more oil than an ordinary waterflood, and that steam injection could yield recoveries "as much as 100 percent greater than by water flood." They also concluded that both the heat requirements for a reservoir and the residual oil remaining in the reservoir after steam injection were independent of the amount of oil originally in place, that short exploitation times were desirable, and that a high percentage of net sand in the reservoir with a high initial oil saturation was desirable. The method assumes that the flood occurs in three concentric cylindrical zones: (1) an inner steam zone, (2) a central hot water zone, and (3) an outer cold waterflood zone. Displacement in the steam zone is based on laboratory-determined residual oil saturations while the hot water and cold water zones use the conventional Buckley-Leverett equations. Although the results shown by Willman et al. are for a radial system flowing out from the well to an assumed external circular boundary, their equations did

Jan 1, 1969

PRESIDENT AND DIRECTOR D.C. JACKLING SAN FRANCISCO, CALIF. PAST PRESIDENTS AND DIRECTORS NEW YORK, N. Y. R. C. ALLEN- CLEVELAND, OHIO VICE-PRESIDENT, TREASURER AND DIRECTOR KARL EILERS-* NEW YORK, N. Y. VICE-PRESIDENTS AND DIRECTORS HENRY KRUMB NEW YORK, N. Y. PAUL D. MERICA . NEW YORK, N. Y. H. G. MOULTON NEW YORK, N. Y. HARVEY S. MUDD Los ANGELES, CALIF. WILFRED SYKES CHICAGO, ILL.

Jan 1, 1938

By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

By Charles Burgess

THE improvement, in the quality of cast iron by means of alloy additions has been a metallurgical accomplishment of recent years. Work in this field has shown that chromium is one of the most effective of such additions but, in general, the influence of chromium has been studied only in. connection with other alloying additions, with irons other than foundry irons, or with relatively high percentages of chromium. The present study was initiated for the purpose of determining the influence of small additions of chromium (0.25 to 1.00 per cent) on the quality and resultant properties of cast irons of various foundry grades. The effect of small chromium additions on cast iron was investigated with particular reference to casting characteristics, hardness vs. section, strength, machinability, heat resistance and structure. MATERIAL TESTED Three separate types of cast iron were investigated as to the effect of small chromium additions. The first series of these irons was prepared from remelted foundry cast iron at the Union Carbide and Carbon Research Laboratories, and the other two -series consisted of cupola melts made under usual operating conditions. The first series was made by melting 30-lb. charges of foundry scrap iron containing - 2.86 per cent carbon, 2.72 silicon, 0.50 manganese, 0.062 sulfur and 0.794 phosphorus in a carbon resistance furnace. The chromium was added as high-carbon ferrochrome just before pouring. The irons were cast at approximately 1250° C. (2282° F.). The analysis and physical properties of these irons are given in Table 1, test 1. The second set of cast irons was made in a cupola in accordance with normal practice, 'the charge containing approximately 42 per cent steel scrap and the chromium additions being made to the ladle. Analysis and tests of these heats are shown In Table 1, test 2. A small amount of copper was present in heat C of this series.

Jan 1, 1932

By D. E. Moore

The strength of a natural serpentinite gouge was measured at 400°C and an effective pressure of 100 MPa. The strength of the gouge decreased with increasing pore pressure to 50 MPa and then was nearly constant between 50 and 125 MPa. The samples at 50-125 MPa pore pressure slid stably, whereas those at 3-25 MPa pore pressure showed stick-slip behavior. Lengthening the pre-heating time to 72,000 s of samples at 100 MPa pore pressure led to increases in both the strength and the likelihood of sliding unstably. With still longer pre-heating times, the strengths decreased again and sliding once more became stable. The strength of the gouge at 3 MPa pore pressure was unaffected by changes in pre-heating time. A possible explanation for the results is that excess pore pressures are being generated in the gouge, causing the true effective pressure to be lower than the apparent value.

Jan 1, 1984

By Carl Davis

A description is given of grinding practice on the Rand and of experiments made to improve that practice. The paper includes a description of the experimental plants and methods and the results obtained. THE first tube-mill on the Rand was put into operation in May, 1904, at the Glen Deep Mine. From that time onwards, tube-mills were added to various plants, although little was known regarding the capacity of a given tube-mill when working on banket ore. Within a few years, however, the so-called standard size (length of shell 22 ft. 0 in. diameter 5 ft. 6 in.) was generally used until the last year or two. Practically the only exceptions were about 30 tube-mills having a length of 16 ft. and a diameter of 6 ft., and a few open-end mills of the roller-supported type. Most of the information obtained during the last 15 years has been obtained with mills of the standard dimensions. The adoption of the tube-mill as an accessory to the stamp mill was rapid; and where 3 tube-mills were working on the Rand at the end of 1904, 244 were in use seven years later.1 By 1910, good practice provided 1 tube-mill for 20 stamps of 2000-lb. falling weight. The horsepower of the motors driving the tube-mills had increased from. 80 to 100 and then to 125 at this date. Broadly speaking, current practice at that date aimed at a final product of which 60 per cent. was suitable for sand treatment and 40 per cent. for slime. The sand grading was +60 mesh, 6 per cent.; +90 mesh, 25 per cent.; -90 mesh, 69 per cent.; and the slime grading -200 mesh, 2 per cent.; -200 mesh, 98 per cent.

Jan 12, 1924

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By L. S. Panyity

The inception of this paper may be traced directly to the various discussions of another paper by the writer1 wherein certain indefinite beliefs and opinions were emphasized as to the relative importance of total sand porosity and the actual size of the openings between the grains. Since publication of that paper it has been possible to study various methods of sand analyses and results that have been obtained under different conditions and actual operations in the field. The purpose of this paper is to indicate the value of screen analysis, especially in areas where repressuring by means of water-flood, air or gas is being used in the partly depleted fields. Sand samples have been analyzed for porosity, saturation and grain size. They are mainly from the Bradford water-flood area, where a great reliance has been put upon such analyses, and where many data are available, A few sand studies are included from fields other than the water-flood area, in order to indicate the possibilities of screen analysis in any field. Examples of various conditions are given in Figs. 1 to 7, which show the porosity, saturation and grain-size analyses of submitted cores or drill cuttings. The generally accepted methods of delineating such sand studies on cross-section paper, known as "core charts" has been employed; with the exception that a method of representing grain size has been evolved which is believed to be the best adapted for this purpose. It differs from the block diagrams generally used, in the employment of a linear section. Percentage of grain-size is represented by the subdivision of a given distance, where the total length represents the whole sample of rock chunk, while the subdivisions indicate the percentages of grains of the different sizes that will pass through the various sieves, through which the samples of crushed sand are sorted to determine the size and amount of the components that make up the aggregate. Thus, on Fig. 1, under the heading of Grain Size, the first samples are composed of grains of the following sizes: 16 per cent. through 120-mesh sieve; 33 per cent. through 150-mesh; 25 per cent. through 180-mesh; 26 per cent, through 200 mesh; a total of 100 per cent. A minus sign is placed before

Jan 1, 1931

By S. K. Bradford

(Pittsburg Meeting, March, 1910.) FOR years past I have traveled in quest of promising mining-properties, over almost impassable mountain-trails to remote places in the mining-regions, usually, many miles from an assay-office. If, upon examination, the formation and the ore-deposit appeared favorable, a quick determination of the value of my samples was necessary, in order that I might take intelligent action with reference to the acquisition of the property. A journey with my samples to civilized regions often meant weeks of delay, and perhaps loss of opportunity. How many, under similar circumstances, have returned with their assay-results from such a journey, only to find that some audacious speculator had " optioned" the property ! True, a first payment could have been made and the chances taken on the results; but experience has taught that rich-looking ore is not of necessity valuable. Personally, I would not hazard a ten-dollar bill on any property without first determining by assay the value of the ore. To carry the usual complete assay-paraphernalia over such mountain-trails was impracticable by reason of the loss of time involved, the great expense of transportation (charged according to weight), and the fact that a few such trips would almost certainly wreck the outfit. For these reasons I began a process of elimination and substitution which finally enabled me to carry, in an ordinary 26-in. valise, sufficient apparatus and supplies for, say, 100 assays of adequate commercial accuracy. My final outfit was as follows: APPARATUS. Small hammer; steel mortar (2.5 in. wide, 3 in. high, with stand sawed off flat, so that it can be used as an anvil and for

Jan 1, 1911

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By W. A. Ver Wiebe

It is becoming increasingly apparent that the State of Kansas contains one of the largest reserve areas for oil exploration in the United States. During the year 1936 no less than 54 new oil pools were discovered by drilling. In addition, seven gas pools were found, which may develop into oil pools when deeper horizons are tested. Several old pools increased their reserves when production was found in lower strata. The data presented in Table 2 indicate that nearly 2000 wells were drilled in the state during 1936. Of these more than 1214 found commercial quantities of oil and at least 61 found marketable quantities of gas. The data are conservative because complete results on drilling are not available for the eastern part of the state. Ellis, Rice and Russell Counties share honors with a total of 10 new pools in each. Barton County is prominent with six pools; while those counties claiming fewer new pools are Clark, Ellsworth, Harvey, McPherson, Ness, Pawnee, Rooks, Stafford and Trego. Important additions to our gas reserves were found in Finney and Haskell Counties, which are north of the extensive Hugoton gas area and may some day be part of it. At the close of the year there were 17,317 wells in the state rating as producers. By far the larger share (14,000) were classed as strippers and allowed to flow 100 per cent of their potential capacity, thus accounting for 33,500 bbl. a day. The remaining wells, capable of producing from 15 up to over 6000 bbl. per day, were limited in output according to these amounts. The largest wells having a potential of from 3000 to 7000 were allowed to flow from 2 to 3½ per cent of their official potential capacity. The percentage rises until wells of 15 to 20-bbl. capacity have a rating of slightly over 83. On the basis of these calculations the total potential capacity of all wells was 1,667,814 bbl., and the daily amount allowed was 175,851. Nine of the pools most recently opened were still unable to market their oil and were classified as "shut-in" pools. Total production for the state for 1936 was somewhat over 58 million barrels. Striking Geological Data Some interesting geological data were uncovered by deep drilling during the year. The most remarkable bit of information is the discovery

Jan 1, 1937

By Verne C. Fryklund, S. Warren Hobbs

The Coeur d'Alene district in the panhandle of Idaho is one of the major lead-zinc-silver producing areas in the world. The value of recorded production to date has exceeded $2 billion. Country rock comprises six formations of the fine-grained, highly siliceous, and slightly metamorphosed Precambrian Belt Series. Small stocks of monzonitic rocks and several varieties of dikes intrude the sediments. The district is at the intersection of a north trending major anticlinal uplift and the west northwest-trending Lewis and Clark line of which the Osburn fault is the dominant feature. The district structure is complicated and comprises folds, some of which are overturned, and a complex of faults of diverse ages and directions of movement. Late Cretaceous stocks but are also probably Cretaceous in age. The productive veins are localized within a series of 12 subparallel, straight mineral belts that trend approximately N65°W and that appear to be controlled by deep fractures in the basement rocks. The mineral belts are in two groups, separated by 15 miles of post-mineralization movement on the Osburn fault. Veins and ore shoots are variously disposed within each mineral belt. Many crop out at the surface, but others apex several thousand feet beneath it. Local controls that influence the position of ore shoots within the mineral belts include the brittle character of host rock attitude of bedding relative to the mineralized fracture, and the amount and direction of movement on faults. Depth appears to have had little effect on the occurrence or type of ore. Ore occurs in a series of steeply dipping replacement veins of relatively simple mineralogy. Six periods of mineralization, ranging from Precambrian to Tertiary in age, are recognized. The productive galena sphalerite-bearing and tetrahedrite-bearing veins-of the main period of mineralization-are younger than the

Jan 1, 1968

By C. D. King

A QUARTER century ago this country was producing an extraordinary quantity of iron and steel, with a decisive influence on the outcome of the first World War. Today this country is again demonstrating its industrial capacity with telling results. If this lapse of time has confirmed the opinion that man learns little from experience with respect to human relationships, at least we can derive some consolation from the knowledge that in the same period we have made huge strides industrially, and particularly in the steel industry. The differences represented by 25 years are striking, and have resulted from a multitude of changes that have contributed to the present-day high state of our pig iron and steel manufacture.

Jan 1, 1944

By B. D. Smith, K. H. Coats

Experiments in which calcium chloride displaced sodium chloride from four cores showed the extent of asymmetry in the resulting effluent concentration profiles. These results provided a check on how validly the mixing process is modeled by a differential (i.e., not finite-stage) capacitance mathematical model. The effluent concentration profile from two consolidated cores exhibited considerable asymmetry, while two unconsolidated cores yielded nearly symmetrical profiles. All runs resulted in breakthrough of the 50 per cent concentration significantly before one pore volume was injected. In addition, velocity appreciably affected the effluent concentration profile from a Torpedo sandstone core. The differential capacitance model matched the data significantly better than a simple diffusion model. The capacitance model allows determination of the amount of dead-end pore space in a porous matrix and the effect of velocity on the rate of diffusion into this space. An experimental program yielding insight into the physical validity of the capacitance effect is described. INTRODUCTION Axial dispersion — the mixing accompanying the flow of miscible fluids through porous media — has been the subject of many relativeiy recent studiesl-13 and a comprehensive review of the topic has been given by Perkins and Johnston.14 This dispersion is of practical interest in studies of the miscible displacement process, fixed-bed chemical reactors, and the adsorption of solutes from a flowing stream onto the surface of a porous medium. In the latter case, the effect of dispersion must be considered when adsorption parameters are determined from the nature of concentration profiles. In general, early studies of dispersion assumed applicability of a simple diffusion equation and were concerned with correlation of the experimentallv determined "effective" diffusion coefficient with system properties over a large range of the latter. Recent have been concerned with the deviations between the asymmetrical effluent concentration profiles observed and the symmetrical ones predicted by the diffusion model. In the present study, effluent concentration profiles were obtained from consolidated and unconsolidated cores. These profiles were compared with those predicted by a differential (i.e., not finite-stage) capacitance model. Solutions to the simple diffusion model, for three sets of boundary conditions, were compared with one another and with the experimental profiles. SUMMARY OF PREVIOUS WORK The reader is referred to Perkins and johnston14 for an extensive review of studies of dispersion in porous media. Many investigators have employed the simple diffusion model characterized by Eq. 1 below: The dispersion coefficient D for unconsolidated systems is correlated by u is interstitial velocity and dp is particle diameter. Since heterogeneity of the sand pack affects the mixing, this equation is also expressed as where a is proportional to the degree of heterogeneity and is about 3.5 for random packs of unconsolidated sand.l4 Eq. 3 holds for 2 For a Do homogeneous (regular) type of packing, should be 1 or less.6 Aris and Amundson6 and Carberry and Bretton consider o to be the number of particle lengths per mixing cell in the finite-stage model. Data from consolidated cores indicate dp to be about 0.36 cm for outcrop rocks, Torpedo sandstone having a reported value of 0.17 cm.15 For v /Do less than about 2, the effect of molecular diffusion must be considered and the total dispersion coeffi-

Jan 1, 1965

By G. T. Murray

The aging behavior of a Cu-Ti (3.2 at. pct Ti) alloy has been followed by electrical resistivity, hardness, and metallographic changes. The resistivity data indicate two principal processes, the first causing a sharp decrease in resistivity, and the second, which occurs over a long period of time, a much smaller rate of decrease. Lamellar nodules, Widmanstätten platelets, and homogeneous continuous precipitation was observed. The Widmanstätten platelets grow at the expense of the latter. When this study was initiated, little information was available on the aging behavior of copper-base titanium alloys. Several articles&apos;-3 that appeared in the early 1930&apos;s showed that these alloys could be strengthened by precipitation, but a detailed study was not made. Within the past year, however, two other more comprehensive studies4&apos;5 have been reported in the literature, one consisting primarily of an investigation of mechanical properties, the other

Jan 1, 1961