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By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By A. S. Eve

IN the spring of 1930, the question was raised as to the possibility of estimating the depth to which the pyrrhotite-nickel deposit at the Falconbridge mine extended in the earth. This body is 7500 ft. long, it dips at 80° to the north, and it is fairly straight with slight sinuosities. Dr. F. W. Lee suggested that it might be possible to solve the problem by measuring the vertical magnetic intensity, with a good magnetometer, both near the surface of the earth and also at a level a 'few feet higher in the air. The writer regarded this suggestion with some scepticism, but it was decided to put the scheme to a prac¬ tical test. In July, 1930, Dr. Lee, Dr. Keys and I ' the writer, with Mr. Joyce and Mr. Belloc as assist¬ ants, made a firm, light wooden platform (Fig. 1) E measuring 4 by 4 ft. on the top, which was 10 ft. above ground. This platform could be moved easily a few yards by four men, and carried across I country in a wagon or by motor truck. Some iron nails were used in its construction, but we were not able to detect their influence on the - Askania magnetometer. Nevertheless, in future work, the use of iron should be completely avoided. Readings were taken along a traverse at right L angles to the orebody, at several stations, both on FIG. 1.-VERTICAL the ground and on the platform. The excess read- ASKANIA MAGNETOM¬ ETER ings, over the dike, as compared with those about 10 ETER ON A FT. HIGH. PLATFORM 800 ft. away, are shown in Table 1. The largest reading, 6.8, is open to suspicion and should be rejected. The depth of the top of the orebody is known by electrical survey, and by actual drilling, to be about 112 to 123 ft., and the covering is sandy glacial drift. Similar readings were taken over a long straight magnetic diabase dike. These also are shown in Table 1. The magnetic vertical intensity is consistently less at the higher level, which is l0 ft. above the lower level.

Jan 1, 1931

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly 100 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposition is accompanied by a change in volume of as much as 5 per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson' found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter5 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to 90 per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced 90 per cent when forged to ½ -in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By Haydn H. Murray, Sam H. Patterson

The term clay is somewhat ambiguous unless specifically defined, because it is used in three ways: (1) as a diverse group of fine-grained minerals, (2) as a rock term, and (3) as a particle-size term. Actually, most persons using the term clay realize that it has several meanings, and in most instances they define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it; therefore, the definition must be general. Clay is a natural earthy, fine-grained material composed largely of a group of crystalline minerals known as the clay minerals. These minerals are hydrous silicates composed mainly of silica, alumina, and water. Several of these minerals also contain appreciable quantities of iron, alkalies, and alkaline earths. Many definitions state that a clay is plastic when wet. Most clay materials do have this property, but some clays are not plastic; for example, halloysite and flint clay. As a particle-size term, clay is used for the category that includes the smallest particles. The maximum-size particles in the clay-size grade are defined differently on various grade scales. Soil investigators and mineralogists generally use 2 micrometers as the maximum size, whereas the widely used scale by Wentworth (1922) defines clay as material finer than approximately 4 micrometers. Some authorities find it convenient to use the term clay for any fine-grained, natural, earthy, argillaceous material (Grim, 1968). When used this way, the term includes clay, shale, or argillite, and some argillaceous soils. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, the term is generally understood by those who use it. Clay is an abundant natural raw material, and it has an amazing variety of uses and properties which will be discussed in this chapter. Clays rank among the leading industrial minerals in both tonnages produced and total value. Their importance is indicated in Table 1, which lists the 1978, 1979, and 1980 production and values according to the US Bureau of Mines (Ampian, 1980). Statistical data summarizing world production of kaolin, bentonite, and fuller's earth are compiled by the US Bureau of Mines (Ampian and Polk, 1981). The total world bentonite production in 1980 was 6,625,204 st of which the United States produced 4,184,619 st. The total fuller's earth produced in the world in 1980 was 1,952,600 st of which 1,534,000 st was produced in the United States. The total world kaolin production in 1980 was estimated at 22,971,000 st. Approximately 13 million tons of this total was produced in two countries, the United States and the United Kingdom. World production data on ball clay, fire clay, and miscellaneous clays are not available. As industrial minerals, clays are a complex group that consists of several mineral commodities, each having somewhat different mineralogy, geologic occurrence, technology, and uses. In this chapter these commodities are organized as follows: (1) bentonite and fuller's earth; (2) kaolin, ball clay, halloysite, and refractory clays; and (3) miscellaneous clay and shale. Bentonite and fuller's earth are grouped together because they are closely interrelated. Though bentonite is a term based on mineral composition and fuller's earth is a term based on use, the two are virtually inseparable, because much, but by no means all, clay sold as

Jan 1, 1983

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

By Floyd C. Kelly

There is an ever-increasing demand for furnaces with controlled atmosphere, due to the large quantities of steel being used in the automotive industry, such as the high-chromium stainless irons, the 18 Cr, 8 Ni stainless iron and low-carbon steel sheets. The difficulties involved in the annealing of such materials, if they are to be kept absolutely free from oxidation, are many. It is possible to bright-anneal these steels in small laboratory hydrogen furnaces, using specially purified hydrogen and taking some additional precautions. In the first place, the insulation, usually of alumina or magnesia, holds small amounts of water vapor, which it is almost impossible to remove completely. Secondly, there is always condensataion of water vapor in the cooling chambers of such furnaces, and with the continuous circulation of the hydrogen gas in the furnace, the water vapor is carried from the cooling chamber back into the heating chamber. This water vapor oxidizes the charge. Lastly, the supply of moisture is made sure by the diffusion of small amounts of air from the atmosphere into the furnace against the pressure of the hydrogen. The oxygen combines with the hydrogen and forms more water. Under such conditions there is little gained by using specially purified gas, because it becomes contaminated after reaching the furnace. Low-carbon Steel If a sheet of low-carbon steel is annealed in such a furnace at 750" C. and allowed to cool with the furnace, an adequate flow of purified hydrogen being maintained all of the time, the steel will come out with a very thin coating of blue oxide. If a similar sheet is annealed at the same temperature and quickly pushed into the cooling chamber, it will come out nearly bright, or perhaps with only the edges slightly discolored. It is difficult to get a piece of steel through a furnace of this type with an absolutely bright surface. This is due to the fact that there are always traces of oxygen or water vapor in the furnace. When the steel is allowed to cool with the furnace, it reaches a critical temperature where the affinity of iron for oxygen is greater than that of hydrogen for oxygen, and the steel comes out discolored. If the steel is pushed from the hot zone

Jan 1, 1931

By Mark Sheppard

DURING the winter of 1937, the writer visited a West Virginia stone quarry at which the overburden is stripped hydraulically. The quarry is in a bed of limestone, about 200 ft. thick, which outcrops on a hillside above a small river; the quarry face is 175 ft. high. The top of the stone is cut in all directions by erosion channels, which are filled with a tough, red clay. Some of the larger channels are 30 ft. deep and 8 ft. wide. The thickness of the clay overburden ranges from a few inches to 10 ft., the average being estimated as less than 3 feet. The topography of the district is rugged, and the hillside above the quarry face is not suited to the use of the usual mechanical methods of moving dirt. Until hydraulicking was started 10 years ago, the over- burden was dug by hand labor, dumped to the quarry floor and transported to the dump in quarry cars. Cleaning deep channels was a slow and expensive process. When hydraulicking was started, the top of the quarry face was over 200 ft. above the level of the river. The pipe line was carried in a semi- circle around the top of the quarry about 200 ft. from the face and about 50 ft. above it. As there is no adequate supply of water above the quarry, the water must be pumped from the river. As quarrying progressed the pipe line was moved until the discharge points are now over 300 ft. above the river. Water is pumped from the river by a four-stage centrifugal pump having a 5-in. intake and a 4-in. discharge. It is direct-connected to a 200-hp., 2300-volt, 1760-r.p.m. induction motor. At 1760 r.p.m. the rated capacity of the pump is 750 gal. per minute under a head of 600 ft. The pump is installed in a house of frame construction on the river bank, about 10 ft. above normal water level, which also houses the pump for the mill-water supply. Above the pumps are hoisting bays into which the motors are raised whenever the river reaches flood stage. An 8-in. suction line, equipped with a strainer and a foot valve, takes the water from a concrete sump at the edge of the river. The pipe line from the pump consists of 1750 ft. of 8-in. spiral steel flanged pipe and 800 ft. of 4-in. spiral steel flanged pipe. The connection from the pump

Jan 1, 1938

By Harry H. Power

The relative merits of air and natural gas as propulsive agents in pressure drive operations have been discussed for a number of years. When air or gas is introduced into the sand, various factors lead the operator to the selection of what he believes to be the proper propelling medium; but when the question of relative drive effect is raised, several physical and chemical premises must be taken into consideration in arriving at a conclusion as to the superiority of one medium over the other. Dow and Calkins1 and Beecher and Parkhurst2 have contributed fundamental experimental work on the effect of dissolved gas in lowering the viscosity and surface tension of crude oil. Herold; and Tickell' have indicated that whatever type of reservoir control obtains, gas plays other important parts in the movement of oil towards the well, namely: 1. The propulsive and expansive force of the gas. 2. The "Jamin effect," or resistance to the movement of oil in a porous media due to the formation of gas bubbles. When quantitative studies are made, parallel conditions must be selected whereby we may say definitely whether air is superior to gas as a driving medium, or vice versa. Examples of similar conditions are not easy to find in the field. However, in the laboratory we can make determinations which may lead to general conclusions when applied to the field. The experimental and research work described here was started at the laboratories of the University of California in January, 1927, and completed in private laboratories at Tulsa, Okla., in February, 1928. The apparatus used was designed especially for the work.

Jan 1, 1929

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By J. D. Mote, A. Rosen, J. E. Dorn

The effect of strain rate and temperature on the critical resolved shear stress for (1100) [1120] prismatic slip was determined for the intermediate hexagonal phase containing about 67 at. pct Ag and 33 at. pct Al. Whereas the flow stress increased only slightly as the test temperature was first decreased below room temperature, a rapid increase inflow stress was obtained with yet greater decreases in temperature from about 240" to 4°K. The effect of both temperature and strain rate on the flow stress over the low-temperature range could be completely rationalized in terms of the Peierls mechanism when the deformation is controlled by the rate of nucleation of pairs of kinks. A few years ago Mote, Tanaka, and Dorn1 observed that the critical resolved shear stress for prismatic slip of a 67 at. pct Ag plus 33 at. pct A1 hexagonal intermediate phase by the (1100)[1120] mode decreased precipitously as the test temperature was increased from 4" to about 160°K. Their results for both basal and prismatic slip are given in Fig. 1. It is obvious that only the flow stress for prismatic slip is strongly temperature-dependent, whereas the flow stress for basal slip is independent of temperature. If the temperature dependence of the flow stress were primarily due to interstitial impurities, it might be expected that they would influence the flow stress for basal slip as well. Since the activation volume at 115°K for prismatic slip was determined to be about 15b3, where b is the Burgers' vector, this thermally activated deformation process was tentatively ascribed as being due to the Peierls mechanism. But the various analyses of the Peierls mechanism then available as formulated by Seeger2 and also by Lothe and Hirth3 did not agree well with the experimental data. Since that time a more realistic theory for the operation of the Peierls mechanism under conditions where the strain rate is determined by the rate of nucleation of pairs of kinks has been presented by Dorn and Rajnak.4 The present investigation was, therefore, undertaken in order to provide the essential data for a careful check on the agreement between this theory and the low-temperature deformation by prismatid slip of the above-mentioned Ag2A1 intermediate phase. EXPERIMENTAL TECHNIQUE Single-crystal specimens so oriented that the [1120] direction and the normal to the (1100) plane were at 45 * 2 deg to the tensile axis were grown from the congruent melting composition of about Ag2Al for the intermediate hexagonal phase by the

Jan 1, 1964

By R. E. Radabaugh, J. M. Brown, J. S. Merchant

The Gilman district is on the northeast flank of the Sawatch Range in central Colorado. It has yielded a total of 10,000,000 tons of ore having a value of over $250,000,000. Paleozoic sediments intruded by a Tertiary quartz latite sill and unconformably overlying Precambrian intrusives and metasediments comprise the country rock of the area. The sediments strike northwesterly and dip 8° to 12° northeasterly. Structures in the Precambrian are related to the Homestake shear zone of the Colorado mineral belt. Only minor folding and faulting occur in the sediments. The principal ore bodies are massive sulfide replacement deposits in carbonate rocks. They consist of long, pipe-like mantos in the completely dolomitized Mississippian Leadville Limestone and funnel-shaped chimneys of copper- silver ore cutting across the Mississippian and Devonian strata. Mineralization is continuous from the chimneys into the mantos. The principal ore bodies are roughly in the shape of a four-tined fork which points up dip. Smaller manto deposits occur in the Cambrian Sawatch Quartzite, and fissure veins are present in the Precambrian rocks. The principal minerals in the mantos are marmatite and galena in a gangue of pyrite and manganosiderite. The chimneys consist of a central core of pyrite with erratically distributed chalcopyrite, tetrahedrite, freibergite, and occasional galena with a shell of zinc ore on the outer margin. Both the chimneys and the mantos are surrounded by imperfect shells of manganosiderite and sanded dolomite. The mineralization is of Laramide age. Hydrothermal alteration affects all rock units to varying degrees. Clay mineral alteration halos occur around the ore bodies. Hydrothermal solutions have developed sanded rock, rubble filled channels, and banded zebra textures, principally in the Leadville Limestone. Structural control of the ore bodies is not well defined. Both the location of the district and the chimneys are probably related to basement structures. The mantos are largely controlled by stratigraphic factors and a pre-Pennsylvanian karst topography in the Leadville Limestone, which were modified by hydrothermal activity, and by weak zones of northeasterly trending faults.

Jan 1, 1968

By Arnulf Muan

PHASE relations in three isothermal sections (l000°, 1100°, 1200°C) of the system Ag-Fe-Pd have been determined as part of a program to develop improved crucible materials for containing low-melting iron silicates at low oxygen potentials. The following experimental method was used: Two- to 3- g samples of each of forty different alloys within the system Ag-Fe-Pd were made up from metals of 99.9 pct purity. The mixed metal powders were contained in a 1-cc crucible of dense recrystal-lized alumina and heated in a protective atmosphere (90 vol pct A, 10 vol pct H2), first to complete melting for approximately 30 min and subsequently at the desired equilibration temperature (1000°, 1100°, or 1200°C) for approximately 24 hr. The samples were then quenched rapidly to room temperature and examined metallographically as well as by X-ray techniques. Unit cell dimensions were compared with standards obtained by study of one-phase alloys of known compositions. The results are summarized in diagrams (a), (b), and (c) shown in Fig. 1. Heavy solid curves outline areas comprising compositions of mixtures consisting of the phases labeled for each area. Mixtures in which liquid is the only condensed phase present are confined to very narrow areas adjacent to the Ag-Pd join at high silver contents. An enlarged, distorted picture of the phase relations prevailing in these areas is shown in the upper-left circular insert. Particular attention is directed toward the misci-bility gap which occupies major parts of the composi-

Jan 1, 1962

By W. E. Hess

AT the Vesta mines of Jones & Laughlin Steel Corp. on the Monongahela River, 35 miles south of Pittsburgh, JCM Joy continuous miners and 6-SC shuttle cars are used for pillar extraction in the Pittsburgh seam. The entire output of the mine goes into coke production for blast furnace operation. Because this coal, which has high metallurgical qualities, is close to the place where it is ultimately used and because supplies with these properties are being rapidly depleted, complete recovery is essential wherever possible. With the introduction of the continuous miner into the Vesta mines, therefore, it was necessary to plan a project which would facilitate development and provide for future total recovery. Use of continuous miners under varying conditions has necessitated changes with regard to roof action, method of development, method of pillar attack, and innovations in mining. In the following pages these changes will be discussed. Prior to the introduction of continuous miners the Pittsburgh seam at the Vesta mines averaged 72 in. of mineable coal, overlain with 12 to 16 in. of draw-slate, which weathers on exposure to air and is not firm enough to be held in place. Immediately overlying the drawslate is a wild or rooster coal, very irregular in thickness, varying from 12 to 30 in. Above the rooster coal the strata consists predominately of shales or lime shales and sandstone. Just before the introduction of continuous miners in the Vesta mines, however, a definite change took place in the character of the roof structure overlying the coal seam, see Fig. 1. Thickness of laminated roof immediately overlying the rooster coal varies with localities and introduces a problem in roof control. In fact, a set of eight main entries being developed in Vesta NO. 4 mine entered an area with so difficult a roof structure that management considered abandoning the section altogether. In this locality the roof consisted of thin alternate layers of roof coals and shales, with an occasional irregular seam of slick slate, the whole being laced with slips, and the coal itself being cut by clay veins and spars. In an effort to overcome some of the difficulties, roof bolting was introduced in 1949. This made it possible to recover coal from an area which otherwise would have been economically unmineable. There have been very few roof bolt failures. When conventional machines were replaced by continuous miners there were changes in the development of butt entries. By these changes it was hoped: 1—to speed development, 2—to provide as much solid coal as possible for the machine on retreat, 3—to avoid the necessity of crossing entries already driven, 4—to facilitate ventilation, 5—to provide a roadway for shuttle car haulage which would eliminate the necessity of running through doors or curtains, 6—to provide better roof control by increasing the distance between the center lines of entries, and 7—to provide more coal when the machine was in position to load.

Jan 1, 1956

By A. T. Tye

WHEN the roughing tables operated in 1923 were abandoned, all the coarse iron pyrite for-merly removed by the tables had to be ground to flotation size, which caused an increased power con-sumption of 2 kw.-hr. per ton. Recently, by increasing the tonnage, this has been reduced to a total of 16.6 kw.-hr. per ton. The cost of repairs has been slightly reduced by using an alkaline circuit instead of the acid mine water used in 1923. Other economies from elim-inating roughing tables and the finishing tables have more than compensated for the extra grinding and the total costs have remained practically the same, until the first part of 1927, when, with increased tonnage, the total cost has decreased to 72 cents and the repair cost to 9 cents. In 1923, with a combined gravity and bulk flotation flowsheet, the grade of concentrate was only 4.38 per cent copper. With preferential flotation this has in-creased to over 17 per cent copper. The tailing has decreased from 0.29 per cent -copper to 0.18 per cent. The copper recovery, instead of decreasing; as might be expected, has increased from 87.4 per cent to, 91.5 per cent. The silver recovery has also increased from 88

Jan 8, 1927

By Greenleaf W. Pickard

The Parral mining district is located in the southern part of the state of Chihuahua in north-central Mexico, in the border area of the physiographic provinces of the Mesa Central and the Sierra Madre Occidental, at an average elevation of 1700 meters. This is one of the most highly productive lead-zinc districts of Mexico. The principal operating units are the Prieta, Santa Barbara and San Francisco mines. The Santa Barbara-San Francisco del Oro area is located 25 kilometers to the southwest of the Prieta mine. It has a system of generally narrow veins in fault zones, entirely in the shale series. The Santa Barbara veins follow long, persistent fractures, while the San Francisco del Oro veins are in relatively short fractures. The Veta Colorada structure, located 5 kilometers to the northwest of the Prieta mine, was a major producer of high grade silver ore with low lead-zinc content during the eary 1900's. It follows a major north-south fault zone in andesite and is noteworthy for a number of wide oreshoots of limited vertical extension along its 10 kilometer length. The Palmilla and Esmeralda mines are on the south end of the Veta Colorada structure. Numerous smaller mines are operating in the Parral area. During the last 45 years the Prieta mine has produced approximately 15,000,000 tons of complex sulfide ore, principally from one single vein. Extensive stoping has

Jan 1, 1970

By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence' gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By B. M. Larsen, W. E. Shenk, T. E. Brower

Shortly after our previous paper on this subject was printed1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100" C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination SO far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E. Apparatus The final form of apparatus we have used is identical with that described and illustrated in our previous paper, except for the substitution for the Globar furnace of a small high-frequency furnace actuated by a vacuum tube oscillator2 0f about 1.5 kw. capacity, and for a slight modification of the containing vessel. This transparent silica vessel is illustrated in Fig. 1 of this paper. Its enlarged portion is about 5 cm. in diameter and 13 cm. long. The silica tube for inlet of hydrogen is fused into this bulb and ends beneath the metal "bucket" holding the steel sample. This sample is in the form of fine millings. The "bucket" is suspended by a platinum wire from the cap of Pyrex glass. The high-frequency

Jan 1, 1934