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By John C. Calhoun, Alfred Chatenever

An exploratory study wap made to examine the possibilities of a visual approach in investigations into microscopic mechanisms of fluid behavior in porous media. Appropriate apparatus and techniques were developed so that microscopic phenomena could be recorded on color movie film as well as be observed visually. The observation flow cells in which tlie fluid behavior studies were made were essentially single-layered matrices of spheres between plates. sometimes all-glass, sometimes all-Lucite and sometimes a combination of the two. The fluids were limited to water and a filtered crude oil. Two flow regimes were observed during the flow of the immiscible liquids: channel flow and slug flow. In the former, transport was effected through stable networks of interconnecting channels; and in the latter, part of the movement took place in the form of slugs. Under certain conditions, flood-front patterns were found to be different depending upon which liquids were the displacing and displaced phases and not depending upon whether the matrix was water-wet glass or oil-wet Lucite. Residual formations of oil and water were observed and are described. Some of the ramifications and significance of the ohservetl phenomena are discussed. INTRODUCTION In recent years considerations of microscopic mechanisms of fluid flow in porous media have taken on greater significance. Much needs to be learned before the fundamentals of petroleum technology are completely established. For example, many unanswered questions exist in connection with relative permeability, displacement phenomena, residua! fluid formations. flow structure, etc.; and further analytical mathematical formulations are seriously indicated. It is hoped that systematic investigations into the microscopic mechanisms connected with the behavior of fluids in porous media will shed some light on some of the problems extant. Until recently microscopic mechanisms have been considered almost exclusively as speculative hypotheses. Within the past few years, however, the problem has been submitted to a limited number of experimental investigations. Nuss and Whiting' made some studies on the pore-space geometry of sandstones and limestones by impregnating cores with an inert plastic and leaching the solid matrices to leave behind plastic models of the pore spaces. SchaeferZ traced pore spaces microscopically through lengths of limestone cores by cutting away thin sections from the exposed faces normal to the line of view. In 1949 two projects were organized in which dynamic flow phenomena were examined microscopically to uncover microscopic mechanisms. One was set up at the Pennsylvania State College where Lowmanb bserved heterogeneous fluid flow phenomena in capillaries. The second was the American Petroleum Institute Research Project 47B at the University of Oklahoma where microscopic studies of dynamic fluid phenomena in synthetic porous matrices have been made by visual observation and cinephotomicrography.' It is with the latter that this paper is concerned. treating the techniques involved and the observations made. TECHNIQUES Observation Flow Cells The observation flow cells formed a focal point in the techniques employed. Essentially, these were matrices composed of a single layer of spheres sandwiched between two flat plates. This design was arrived at after a series of pre-

Jan 1, 1952

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By H. D. Keiser

Minor industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz, and nonfuel gases (air, helium, carbon dioxide). Alum Minerals The natural alums comprise a group of hydrated double sulfates, the most important of which are potash alum, KAI(S04)2.12H20, the "alum" of popular usage; ammonium alum, (NH4)AI(SO4)2, known mineralogically as tschermigite; and soda alum, NaAI(SO4)2.12H20. Kalinite, KAI(SO4)2.11H20, and mendozite, NaAl(SO4)2, 11H20, are fibrous monoclinic alums, distinct from the isometric species potash alum and soda alum.4 Alunite, KAI3(S04)2(OH)6, also known as alumstone or alum rock, has been used as a raw material in the manufacture of alum since early times. All the natural alums are highly soluble and occur as surface evaporation products in arid regions or in sheltered places. Potash alum, together with the other natural alums, commonly occurs as an efflorescence or crevice filling in argillaceous rocks and brown coals that contain disseminated pyrite or marcasite. The mineral is derived by the action of sulfuric acid, formed during the weathering of the sulfide, upon alkali-rich aluminum silicates. Ammonia alum is found chiefly in lignite or broad-coal beds and bituminous shales. Alunite is most commonly associated with acid volcanic rocks, where the rock has been largely altered and alunite formed owing to the presence of sulfuric acid solutions or vapors. Aluminum sulfate, which for most uses is the essential ingredient of alum, may be found in saline residues resulting from the evaporation of natural water and may be formed by the action of acid waters upon aluminous rocks. A deposit of natural potash alum occurs in an irregular network of veins associated with sulfur in rhyolite in Esmeralda County, Nevada, about 35 miles west of Tonopah and 10 miles north of Silver Peak. Alum was recovered at a plant operated on the property between 1920 and 1923 by crushing the ore to ¾ in., grinding to minus 80-mesh, and counter-current leaching; the resulting alum solution was then filtered and crystallized. Alunite was of much interest during World War I as a source of potash and during World War II as a source of alumina. The wellknown deposits at Tolfa, Italy, are veins in trachyte and have been the basis of alum manufacture there since the middle of the fifteenth century. Pure alunite is insoluble in water and in common acids, but if it is heated to 500°C it loses its water of hydration, and the residue consists largely of anhydrous potash alum, part of which is readily soluble in water or acids. If the heat is increased beyond 500°C, most of the sulfur combined with the alumina is released as oxides and the residue consists of potassium sulfate and alumina. Thus, either potash alum (and aluminum sulfate) or potassium sulfate and alumina may be made. In the

Jan 1, 1960

By Victor Formanek, Paul Chataignon, Maurice Rey

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By D. R. Hay, E. Scala

STUDIES of structure-sensitive properties, especially mechanical behavior, have shown that grain and subgrain structure play an important role. The mechanical properties of tungsten, in particular, are sensitive to the nature of the intergranular structure. Substructure and dislocation networks in single-crystal and polycrystalline tungsten have been studied by Nakayama et al.' Various orders of substructure were observed ranging from a microscopic first order (grain diameter: 2 to 8 mm) to a microscopic second order (grain diameter: 50 to 300 p), and, within the latter, dislocation networks forming an even smaller order of substructure. In their single crystals, grown by arc fusion, the degree of misorientation in each order was small: 16'3OU, -11, and -10" for the first-, second-, and third-order substructure, respectively. To study the properties of polycrystalline tungsten, powder metallurgy tungsten is generally used. However, in a mechanical property investigation, the zone-melted or arc-fusion crystals are more desirable than the powder metallurgy product due to their higher purity and absence of porosity and other defects inherent in consolidation by powder metallurgy. Grain boundaries can also be produced in melted stock by working and recrystallizing. However, material with subgrain mis orientations of the order of several degrees (high-angle substructure) has not been reported previously and is the subject of this communication. Crystals were grown by electron-beam, floating-zone melting. The starting material, Sylvania Pure-tung welding rod, was given one zone pass at a traversal rate of -2 mm per min. Through control of the zone temperature, it was possible to influence the degree of crystal perfection. By maintaining the zone at a high degree of superheat, high-perfection crystals could be grown. However, at temperatures only slightly above the melting point, the zone-melted crystals contained a high-angle substructure. A sensitive control of the zone temperature was not possible due to the difficulty of estimating the temperature of the zone and of providing a constant supply of power to the sample. Therefore, an empirical method, using the shape of the molten zone as a criterion, was adopted as an indication of temperature. At high degrees of superheat, the surface tension of the molten zone decreases and a neck forms at the top of the zone, whereas at low zone temperatures the diameter of the zone remains reasonably uniform. Although it was not possible to obtain a continuous variation of misfit angle, the conditions could be directed toward the growth of either high- or low-angle substructure by maintaining only a slight neck in the zone (sufficient to establish that it was molten) or a well-necked zone, respectively. Mass spectrographic analyses of both types of material revealed no significant differences in the concentrations of their impurities. The degree of misorientation at high angles was obtained by measuring the angular spread of spots corresponding to a single reflection on a Laue back-reflection photograph. Fig. 1 shows a typical Laue back-reflection photograph of a crystal with a 3-deg spread. By measuring the angular deviation of the spots corresponding to a single reflection from the mean center of the spots around which constant angular deviation contours were drawn, an average angular spread of misfit could be calculated. The angular average was weighted by the number of spots observed in each angular interval. At angles greater than 5 to 6 deg the spots from different reflections begin to overlap, and cannot be associated with a particular reflection. Laue back-reflection photographs taken at different locations on samples .with approximately 3-deg spreads showed only a small difference in angular misorientation, less than 8' of arc, within individual specimens. The microstructure was examined using Berg-Barrett X-ray extinction contrast microscopy. Berg-Barrett photographs taken directly on the as-grown surface, Fig. 2, show an essentially equiaxed subgrain structure of -0.1 mm in average grain diameter in both high- and low-angle crystals. Fig. 2(a) is a photograph of a sample with a low misfit angle and Fig.

Jan 1, 1968

By Maurice Rey, Victor Formanek, Paul Chataignon

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By W. B. Mather

A RKANSAS is not only a geologist's paradise, but Ait is also particularly fortunate in possessing a wide variety of mineral resources. The future mineral production and mineral industry of Arkansas, like the other states in Mid-America, will probably depend to a large degree on efforts to increase the exploitation of the non-metalliferous deposits of the state. The term nonmetalliferous, as used in this paper, embraces all types of mineral deposits, except fuels, water, and those deposits from which, after bene-ficiation, metals are ultimately derived. For example, bauxite is the ore of aluminum, but a considerable portion of the bauxite mined eventually is employed in the production of nonmetallic alumina, an important oxide in the abrasive and ceramic industries. The bulk of the production, however, becomes metallic aluminum and therefore this type of mineral resource is considered metalliferous and is omitted from this paper. Arkansas' nonmetalliferous deposits are of many different types, too numerous to discuss in detail in a single paper; therefore, only their salient features are presented. Many types of deposits such as limestone, glass sand, novaculite, shale, and sandstone are exposed over wide areas, providing inexhaustible reserves. Other types of deposits, such as barite and tripoli, contain large reserves which certainly are not unlimited. Still other types of deposits, such as celestite, kaolin, and vermiculite, appear to occur in small isolated deposits containing relatively small reserves. Of course, all of Arkansas' nonmetalliferous deposits probably have not as yet been recognized, nor have all of the known deposits been prospected, tested, and evaluated. Various types of deposits are too low grade or too limited in extent to be profit- ably produced by today's standards. In the case of other deposits, the known uses are few in number, thus acting as a retarder to their development. Due to anticipated technologic advancements, the future demands of industry are not expected always to be the same as they are today, and therefore idle deposits or those of current limited production may readily become the important revenue producers of the future. The types of nonmetalliferous deposits discussed here include: clays, shales, and slates; silica deposits including glass sand, novaculite, tripoli, sandstone, chert, and quartz crystals; limestone and dolomite; barite; gypsum; celestite; nepheline syenite; green-sand; phosphate; vermiculite; fuller's earth; ben-tonite; diamonds; sand, and gravel. The location of the various types of deposits are presented on the accompanying map (fig. 1). Symbols indicate the general area of occurrence. Many deposits, such as limestone, shale, novaculite, and so on, are represented by formations which could only be properly shown on a geological map. In these instances only active deposits or those of exceptional merit are indicated by symbols on the map. A general northeast-southwest line divides the interior highland from the Gulf Coastal and Mississippi Alluvial Plains of south and east Arkansas. The data presented in this paper are only a surnmary of a portion of a more comprehensive survey and study of the natural resources of the entire state.' The study was sponsored and underwritten by the Arkansas Power and Light Co., Little Rock, as a public service to the state and its residents. Permission to present some of the data and conclusions resulting from the survey is gratefully acknowledged. Table I, prepared by the Arkansas Geological Survey from state severance tax records, presents the annual production secured from Arkansas nonmetalliferous mineral deposits. Clays, Shales, and Slates Clays: It is realized that each method of classifying clays is prone to criticism. In this paper, Arkansas' clays of potential value are arbitrarily

Jan 1, 1951

By F. R. Zacher

Unmined blocks in the Sewickley seam, surrounded by worked out areas, have been found to transmit overburden oads through the interval strata to the Pittsburgh seam workings 90 ft below. Operating experiences under these conditions are described in this paper. IT has always been understood, in northern West Virginia where both the Pittsburgh and Sewickley seams are mined, that pillaring or splitting in the lower Pittsburgh seam could break the interval strata and make mining in the overlying Sewickley difficult or impossible. In some instances, however, mining methods practiced in the overlying Sewickley have reversed the problem, resulting in a shifting of the intermediate layer and destroying valuable acreages of the Pittsburgh seam below. The Pittsburgh seam in this area is, on the average, 102 in. thick. About 18 in. of low-quality head coal are left for roof protection as it is mined. Immediately over the coal are two draw slates, two rider seams, and a good hard black shale, locally called black rock, which serves as a permanent roof where draw slates and riders are taken down on certain main haulroads. In most areas mined in this seam in the past the bottom has been satisfactory but soft. However, in areas now being mined by the Christopher Coal Co. in Monongalia County the bottom is very hard and unyielding. The Sewickley seam, lying 85 ft above the Pittsburgh, will average nearly 70 in. in thickness and is overlain by massive shales and sandstones. Much of the seam is mined only down to the "sheep skin," a hard band about 4 in. above the bottom, which is composed of relatively hard shale. Fig. 1 shows a typical cross-section through the Pittsburgh and Sewickley seams in the area being discussed. The thin Redstone seam is not deep-mined but is stripped in some locations where it outcrops. Most of the Sewickley seam in the Morgantown areas has been mined out from 10 to 30 years. There are at present only two large mines and five or six others of small production operating in that seam. Mining systems in the past were generally of the room and pillar type with some full pillar extraction. This seam in the Scott's Run area was operated by as many as thirty or forty different companies at one time, during an era beset with strikes, market failures, and depressions. Most of the barrier pillars along the many main haulroads were abandoned, and blocks of Sewickley coal that would be fully recovered with today's machinery were left unmined when conditions became anything less than favorable. Consequently the mined-out Sewickley is spotted throughout with solid blocks varying in size from 100x100 ft to 200x400 ft and larger. It is these unmined Sewickley blocks surrounded by worked-out portions that have caused transmissions of roof stresses to underlying Pittsburgh mining areas, see Fig. 2, resulting in untold difficulty. As the Christopher Coal Co. operates both the Pittsburgh and Sewickley seams, accurate maps of workings in both seams are readily available and are regularly consulted. The first Pittsburgh squeeze attributed to overlying Sewickley blocks occurred in the Arkwright mine, where a shuttle car crew was developing a section consisting of seven panel headings. These entries were being driven in solid coal 3400 ft from the nearest worked-out Pittsburgh area. As mining advanced it was noticed that certain ribs began to slough and certain areas to show signs

Jan 1, 1953

By W. B. Mather

A RKANSAS is not only a geologist's paradise, but Ait is also particularly fortunate in possessing a wide variety of mineral resources. The future mineral production and mineral industry of Arkansas, like the other states in Mid-America, will probably depend to a large degree on efforts to increase the exploitation of the non-metalliferous deposits of the state. The term nonmetalliferous, as used in this paper, embraces all types of mineral deposits, except fuels, water, and those deposits from which, after bene-ficiation, metals are ultimately derived. For example, bauxite is the ore of aluminum, but a considerable portion of the bauxite mined eventually is employed in the production of nonmetallic alumina, an important oxide in the abrasive and ceramic industries. The bulk of the production, however, becomes metallic aluminum and therefore this type of mineral resource is considered metalliferous and is omitted from this paper. Arkansas' nonmetalliferous deposits are of many different types, too numerous to discuss in detail in a single paper; therefore, only their salient features are presented. Many types of deposits such as limestone, glass sand, novaculite, shale, and sandstone are exposed over wide areas, providing inexhaustible reserves. Other types of deposits, such as barite and tripoli, contain large reserves which certainly are not unlimited. Still other types of deposits, such as celestite, kaolin, and vermiculite, appear to occur in small isolated deposits containing relatively small reserves. Of course, all of Arkansas' nonmetalliferous deposits probably have not as yet been recognized, nor have all of the known deposits been prospected, tested, and evaluated. Various types of deposits are too low grade or too limited in extent to be profit- ably produced by today's standards. In the case of other deposits, the known uses are few in number, thus acting as a retarder to their development. Due to anticipated technologic advancements, the future demands of industry are not expected always to be the same as they are today, and therefore idle deposits or those of current limited production may readily become the important revenue producers of the future. The types of nonmetalliferous deposits discussed here include: clays, shales, and slates; silica deposits including glass sand, novaculite, tripoli, sandstone, chert, and quartz crystals; limestone and dolomite; barite; gypsum; celestite; nepheline syenite; green-sand; phosphate; vermiculite; fuller's earth; ben-tonite; diamonds; sand, and gravel. The location of the various types of deposits are presented on the accompanying map (fig. 1). Symbols indicate the general area of occurrence. Many deposits, such as limestone, shale, novaculite, and so on, are represented by formations which could only be properly shown on a geological map. In these instances only active deposits or those of exceptional merit are indicated by symbols on the map. A general northeast-southwest line divides the interior highland from the Gulf Coastal and Mississippi Alluvial Plains of south and east Arkansas. The data presented in this paper are only a surnmary of a portion of a more comprehensive survey and study of the natural resources of the entire state.' The study was sponsored and underwritten by the Arkansas Power and Light Co., Little Rock, as a public service to the state and its residents. Permission to present some of the data and conclusions resulting from the survey is gratefully acknowledged. Table I, prepared by the Arkansas Geological Survey from state severance tax records, presents the annual production secured from Arkansas nonmetalliferous mineral deposits. Clays, Shales, and Slates Clays: It is realized that each method of classifying clays is prone to criticism. In this paper, Arkansas' clays of potential value are arbitrarily

Jan 1, 1951

By F. W. Warnaars

The Los Bronces copper deposit is located on the west side of the Andes Mountains in central Chile about 54 km (34 miles) northeast of Santiago. The deposit consists of a hydrothermal breccia complex that was emplaced in the western part of an earlier porphyry copper mineral system. This system exhibits propylitic, sericitic, silicic to potassic hydrothermal alteration with disseminated and stockwork copper-molybdenum sulfide mineralization over an area of about 12 km2 (5 sq. miles). The Rio Blanco Mine, about 800 m (0.5 miles) east of Los Bronces, is an underground block caving mine located in the central part of this system. The mineralization at Rio Blanco is characterized by one of the highest primary copper grades known for porphyry copper systems. Present mining at Los Bronces is from an open pit located in the northern part of a hydrothermal complex that is composed of at least seven different copper-bearing tourmaline breccia pipes. Together these pipe form one large contiguous body about 2 km (1.2 miles) long and 0.7 km (0.4 miles) wide at the surface. This body crops out at elevations of between 3.5 and 4.1 km (2 and 2.5 miles) above sea level. Each breccia pipe has a characteristic shape, matrix, type and degree of mineralization and alteration. Quartz, tourmaline, specularite, anhydrite, pyrite, chalcopyrite, sericite, chlorite, and rock flour are present in significant quantities in most breccia matrices. The clasts consist mainly of quartz monzonite, andesite, and minor amounts of quartz latite porphyry. The seven different breccia pipes are identified, from oldest to youngest, as Ghost, Central, Western, Infiernillo, Fine Gray, Anhydrite, and Donoso. The breccias coalesce, interfinger, or display gradational contacts. In places they form sharp contacts with each other and with the surrounding intrusive or volcanic host rocks. Early breccias are disrupted or cut by subsequent breccia events. Explosive emplacement was followed by collapse after the release of hydrothermal pressures. The Los Bronces breccia complex has sharp contacts with the surrounding intrusive stock and andesites. These contacts dip inward on the north, west, and south margins. The eastern contact is nearly vertical and/or dips slightly outward and suggests a westward tilting of the body of about 15° after emplacement. The breccia complex is not fully explored at depth, but is known to extend at least below the 3 km (2 mile) elevation in its central eastern part, about 1 km (0.6 miles) below the highest breccia outcrop. Primary copper sulfide minerals are most abundant in the Donoso and Infiernillo breccias where the matrix consists mostly of tourmaline, quartz, sulfides, specularite, and/or chlorite with minor amounts of rock flour, sericite, and clay. The volume of the matrix material is mostly smaller than in the other breccias. Secondary enrichment enhanced the primary copper grade in the southern two-thirds of the Los Bronces breccia complex and in much of the surrounding porphyry system. Primary grades of 0.3% to 0.5% copper have been enriched to approximately 0.9%. This enrichment may extend from surface outcrops to a depth of more than 500 m (1, 640 ft) in more permeable parts of the breccia complex. A leached and oxidized capping of variable thickness covers a large part of the enriched layer and exceeds 300 m (984 ft) at one location. The shape and depth of the enrichment blanket and the capping suggest that the enrichment process is still active.

Jan 1, 1983

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

By N. K. Chen, R. Maddin

In the extension of molybdenum single crystals at room temperature, the slip planes were found to be of the type (1101; the slip direction <111>. Theories of plasticity of body-centered cubic metals have been examined, and an explanation based upon planes of highest atomic density seems plausible to explain the plastic behavior of molybdenum single crystals. IN body-centered cubic metals, slip has been reported to occur on several planes; these are of the type {110), {112), and (123). Andrade has correlated&apos; the operative slip planes in body-centered cubic metals with the testing temperature relative to the melting point. In this correlation, if T is the absolute temperature at which slip takes place and Tm the absolute melting point, then the acting slip planes in body-centered cubic metals may be arranged as shown in Table I. However, deviations from this correlation have been reported in iron and iron-silicon alloys2 and also in molybdenum deformed at a temperature around 2400°C." In the case of iron and other body-centered cubic metals or alloys in which all three slip planes have been reported to be active at any one temperature, the crystallographic mechanism of slip is not well understood. Numerous investigators in this field have assumed that the resolved shear stress is a deciding factor. Such considerations were given by Gough in his experiments with repeated torsion of iron single crystals4 and recently by Opinsky and Smoluchowski in their study of iron-silicon alloys," and will be dealt with later in this report. A third possibility is that slip lines in body-centered cubic metals may be formed by alternate slip on nonparallel (110) planes and not by slip on any plane of higher indices. This was advanced by Elam in the case of ß brass." Since (1101 planes are planes of highest atomic density in the body-centered cubic structure, this hypothesis would be in accordance with the plastic behavior of metals in other systems, namely, face-centered cubic and hexagonal close-packed. Experimental evidence in support of this hypothesis is lacking. Nevertheless the work of Barrett, Ansel, and Meh12 has definitely demonstrated that the slip resistance on {110} planes in iron is very much smaller compared with that on (112) and (123) planes. In the present investigation, molybdenum single crystals were carefully documented as to the operative slip planes and lattice reorientations after plastic extension at room temperature. In three crystals studied, (110) planes were found to be active invariably rather than the (112) planes, which were previously reported for molybdenum at this temperature&apos; and predicted by Andrade&apos;s theory.&apos; In two other cases (112) and (123) planes seemed to operate together with (110) planes as active slip planes. However, it is believed, after careful analysis of crystallite and lattice rotations, that slip on (112) and (123) planes may be spurious. Particular reference will be made to the formation of asterism, lattice rotation, and crystallite rotation in an attempt to show that slip apparently observed on {1121} and (123) planes is actually slip on nonparallel {110} planes. Materials and Treatment Sintered molybdenum rods ? in. in diam, obtained from the Fansteel Metallurgical Co., were reported to have a purity of 99.9 pct.* One specimen, Mo-13, ¼ in. in diam, was supplied by Westinghouse Electric Corp. Single crystals were prepared, using the technique devised by Chen, Maddin, and Pond." Mo-13 was ¼ in. in diam x 7 in. long with a reduced gage section of 0.200 in. in diam x 3 in. long. The center of

Jan 1, 1952

By B. Wilhelmi, W. H. Somerton

Simultaneous measurement of pore and elastic properties of socks under a wide range of triaxial stress conditions may be made with equipment and methods developed in this paper. Tests were run on three outcrop sandstones at several confining pressures and axial stresses up to approximately 80 percent of failure stress. The greater reduction in porosities and permeabilities occurred in the hydrostatic loading portion of the stress cycle, but substantial reductions in both properties did occur upon application of deviator (triaxial) stress. Triaxial elastic moduli were calculated from strain gauge measurements. Both Young&apos;s moduli and shear moduli were found to increase with increasing confining pressure. Poisson&apos;s ratios increased with axial stress but showed no consistent change with confining pressure. Only very general relations were observed between pore and elastic properties. The lesser decrease in porosity and permeability at higher stress values is related to increase in rigidity of rocks at higher stresses. INTRODUCTION Many investigators have studied the effects of hydrostatic stress on the properties and behavior of rocks. A few have studied the effects of triaxial stress fields on individual physical properties of rocks. To our knowledge no one has measured simultaneously pore and elastic properties of rocks under a wide range of triaxial stress conditions. This is the purpose of this work. Rocks exist in the subsurface under what Jaegerl refers to as "polyaxial" stress conditions (all principal stresses unequal). When two of the three principal stresses are equal, this is referred to as triaxial loading. The triaxial method of loading is most commonly used in modern testing work because experimental difficulties in measuring physical properties of rocks are greatly reduced over polyaxial testing. Although triaxial loading may not reproduce subsurface conditions precisely, subsurface stress conditions are never known precisely anyway. Triaxial testing would seem to be more realistic than testing under hydrostatic loading (all principal stresses equal) for application of results to subsurface problems. The objectives of this work were threefold: (1) to develop methods of measuring simultaneously pore and elastic properties of rocks under triaxial stress conditions, (2) to determine whether changes in these properties are of sufficient magnitude to be considered in subsurface calculations and (3) to attempt to relate changes in pore properties and elastic properties since they will have been measured at the same time under identical loading conditions. REVIEW OF EARLIER WORK PORE PROPERTIES Several investigators have studied the effects of stress on the physical properties of rocks. Fatt and Davis2 showed the reduction of permeability of rock with hydrostatic loading. McLatchie et al.3 and Knutson and Bohor4 related permeability reduction to compessibility of reservoir rock, again under hydrostatic loading. Wble,5 and later Redmond,6 evaluated the effects of applied radial pressure on conductivity, porosity and permeability of sandstones. In this latter work, no axial stress was applied. Dobrynin7 reviewed much of the previous work done . on the effects of overburden pressure on physical properties of rocks. He concluded that changes in physical properties are controlled to a large extent by pore compressibility of the rock. Several sets of curves developed from empirical relations are presented. These curves permit estimation of change of properties with net overburden pressure, knowing the pore compressibility and porosity of the rock. Net overburden pressure is defined as (Pe - 0.85 Pi ) where Pe is the

By A. D. Marlin, A. J. Gentile, E. F. Jordan

Metallurgical changes in SAE 52100 ball-bearing components resulting from overload testing are described. Changes in microstructure, hardness, and resiclctal stresses crre discussed zuitlz re.ference to material cleanliness obtained by various steel-melting practices and are compared with work by otlzer investigators. Evidence is presented to show that the initialion and development of microstruc-tural alterations are characterized by two separate reactions: the appeavance of a "dark etchingJ&apos; constituent, and "gray lines" or a light etclzing constituent. The dependency of these tzvo reactions on material cleunliness, running tirne, and contact stresses is discussed and a failure mode related to material cleanliness and microstructural transformation is proposed. THE study of ball- and roller-bearing contact fatigue has been paced by a strong emphasis on bears ing application performance. Particular attention has been paid to conditions that effect the spalling-type failure that is characteristic of rolling contact fatigue in through-hardened components. Some of the conditions investigated are lubrication and atmosphere,1-3 material characteristics and finish,475 and speed and design fa~tors."~ A typical spalling-type failure is shown in Fig. 1. The arrow shows the motion of the ball relative to the inner-ring race surface. The leading edge of the spall is usually sharper than the trailing edge. The race surface near the trailing edge also shows small dents caused by debris from the spall. In this type of testing very little metallurgical investigation is done on failed bearings. Emphasis is placed on test conditions and statistical analyses of endurance data. More basic work has been done relating micro-structural changes to fatigue performance. Dyer" and Wood, Cousland, and sargant9 have used mostly simple materials, such as single crystals and single-phase polycrystalline specimens, under simple alternating strain to identify a systematic process of fatigue damage. drutowski" was concerned primarily with the relationship between steel structure, contact stress, and energy losses in rolling contact. dones11 and Bush, Grube, and Robinson12 utilized changes in microstructure and residual stress in overload-tested rolling contact elements as a means of investigating the fatigue process. Work is being done on an ASME-sponsored contract,13 using both simple and complex materials, but there is still a long way to go before such theories as pore and void growth in simple structures can be applied to the relatively complex bearing steel microstructure. The purpose of this paper is to report on an investigation into the effect of steel cleanliness on the structural alteration and residual stress changes found in overload-tested ball bearings. Using these results and those of previous investigators, we will propose probable failure mechanisms in both overload- and normal load-tested ball bearings.14,15 PROCEDURE Ball bearings? 3208 size, were fabricated from SAE 52100 steel obtained by five different melting practices. The melting practices, chemistry, and inclusion ratings for the five lots of steel are summarized in Tables I and 11. The nonmetallic inclusion ratings were determined by the Jernkontoret method described in ASTM E45-51 Method A. This technique consists of microscopically examining a series of polished samples taken from specified locations in the ingots, billets, or bars. Each sample is surveyed at XlOO magnification and the inclusion types and sizes are compared to standard fields. Because of the nature of these ratings all values in Table I1 are rounded to the nearest half. The elec-

Jan 1, 1965

By F. R. Zacher

Unmined blocks in the Sewickley seam, surrounded by worked out areas, have been found to transmit overburden oads through the interval strata to the Pittsburgh seam workings 90 ft below. Operating experiences under these conditions are described in this paper. IT has always been understood, in northern West Virginia where both the Pittsburgh and Sewickley seams are mined, that pillaring or splitting in the lower Pittsburgh seam could break the interval strata and make mining in the overlying Sewickley difficult or impossible. In some instances, however, mining methods practiced in the overlying Sewickley have reversed the problem, resulting in a shifting of the intermediate layer and destroying valuable acreages of the Pittsburgh seam below. The Pittsburgh seam in this area is, on the average, 102 in. thick. About 18 in. of low-quality head coal are left for roof protection as it is mined. Immediately over the coal are two draw slates, two rider seams, and a good hard black shale, locally called black rock, which serves as a permanent roof where draw slates and riders are taken down on certain main haulroads. In most areas mined in this seam in the past the bottom has been satisfactory but soft. However, in areas now being mined by the Christopher Coal Co. in Monongalia County the bottom is very hard and unyielding. The Sewickley seam, lying 85 ft above the Pittsburgh, will average nearly 70 in. in thickness and is overlain by massive shales and sandstones. Much of the seam is mined only down to the "sheep skin," a hard band about 4 in. above the bottom, which is composed of relatively hard shale. Fig. 1 shows a typical cross-section through the Pittsburgh and Sewickley seams in the area being discussed. The thin Redstone seam is not deep-mined but is stripped in some locations where it outcrops. Most of the Sewickley seam in the Morgantown areas has been mined out from 10 to 30 years. There are at present only two large mines and five or six others of small production operating in that seam. Mining systems in the past were generally of the room and pillar type with some full pillar extraction. This seam in the Scott&apos;s Run area was operated by as many as thirty or forty different companies at one time, during an era beset with strikes, market failures, and depressions. Most of the barrier pillars along the many main haulroads were abandoned, and blocks of Sewickley coal that would be fully recovered with today&apos;s machinery were left unmined when conditions became anything less than favorable. Consequently the mined-out Sewickley is spotted throughout with solid blocks varying in size from 100x100 ft to 200x400 ft and larger. It is these unmined Sewickley blocks surrounded by worked-out portions that have caused transmissions of roof stresses to underlying Pittsburgh mining areas, see Fig. 2, resulting in untold difficulty. As the Christopher Coal Co. operates both the Pittsburgh and Sewickley seams, accurate maps of workings in both seams are readily available and are regularly consulted. The first Pittsburgh squeeze attributed to overlying Sewickley blocks occurred in the Arkwright mine, where a shuttle car crew was developing a section consisting of seven panel headings. These entries were being driven in solid coal 3400 ft from the nearest worked-out Pittsburgh area. As mining advanced it was noticed that certain ribs began to slough and certain areas to show signs

Jan 1, 1953

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of- liquid Mg-Pb allojs have been determined by an isopiestic method from 18 to 42 at. pct Pb and by a thevmodynumic analysis of the phase diagram frofiz 0 to 100 at. pct Pb. In the overlapping composition range the magneszupn activity values derived by the two methods are in excellent agreement, thus mutually supporting the correctness of the Mg-Pb phase diagram previously determined by the authors and of the acticitzes deriz~ed isopiestically. SEVERAL studies have been made of the thermody-namic properties of liquid Mg-Pb alloys. Wagner and Engelhardt,1 Lantratov,2 Knappwost,3 Sryvalin et al.* and Wilson5 used the electromotive-force method, Scheil and Wolf8 and Schmahl and Sieben" applied the transpiration technique, and the present authors8 utilized the phase diagram to determine the activity of magnesium in the Mg-Pb system. The results of these studies are not in very good agreement and could not be incorporated into a general systematic analysis of the thermodynamic properties of the homologous series of the Mg-Group IV B systems Mg-Pb,8 Mg-Sn,° Mg-Ge,10and Mg-Si.11 The thermodynamic properties of the Mg-Pb system were therefore re investigated by an isopiestic technique which has been developed for similar studies in the Mg-SnB and Mg-Ge10 systems- Lead specimens, contained in iron or graphite crucibles, were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure to form alloys of compositions which depended on their temperatures, the temperature of the magnesium vapor source, and the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE Magnesium (Dominion Magnesium Ltd., Toronto, Canada) of 99.99+ pct purity and lead (American Smelting and Refining Co.) of 99.999 pct purity were used. In the early experiments, Runs 2 and 3, the alloys were contained in uncovered high-purity iron crucibles. Alloys formed in the uncovered iron crucibles had to be chemically analyzed owing to the slight volatility of lead under the imposed experimental equilibration conditions. The compositions of these alloys were determined by a gravimetric analysis of lead as lead chromate. To avoid this problem, the remaining runs were made in covered graphite crucibles machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non- i reactivity of graphite with lead and magnesium has been previously established,&apos; and the experimental procedure has been described in full detail.&apos; In the runs using covered graphite crucibles it was found that the weight increases of the crucibles and their contents after equilibration equaled the magnesium contents of the alloys within the accuracy of the chemical analysis (i0.3 at. pct Pb). Clearly, the small lid openings of the graphite crucibles prevented significant lead losses during a run, and the weight increase was therefore taken as the magnesium content of the alloys. EXPERIMENTAL RESULTS At thermodynamic equilibrium the magnesium partial pressure of the specimens equaled that of the reservoir. Since the magnesium reservoir was always maintained at the temperature minimum of the system, the activity of magnesium of any specimen was given by the ratio of the magnesium reservoir pressure to the vapor pressure of pure magnesium at the specimen temperature. The standard state was chosen as liquid magnesium and the vapor pressure of liquid magnesium

Jan 1, 1968

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. &apos;This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir&apos;s producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.&apos;.&apos; The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,&apos; experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958