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By T. M. Geffen, H. N. Hall

One-third to one-half of the original oil is left in most reservoirs even after thorough gas driving or waterflooding. In contrast, essentially all of the oil contacted con be recovered by flooding with a solvent (a fluid miscible with the reservoir oil). It is not economical to fill a reservoir with solvent since the value of the solvent would very likely exceed that of the oil. A practical method would be to inject a small bank of solvent to displace the oil. This solvent bank in turn could be driven through the rock by a less valuable scavenging fluid, such as natural gas which is also miscible with the solvent. Such a method of oil recovery was studied in the laboratory using long (up to 95 ft) core systems. It was found that, as the solvent moves through the reservoir, the front end of the solvent bank becomes mixed with the oil and forms a relatively short mixing zone between undiluted crude oil and pure solvent. An engineering correlation was obtained which can be used to predict the length of this zone. Displacement of the solvent by natural gas can be achieved with complete miscibility (above the critical pressure of the gas-solvent system at reservoir temperature) or with partial miscibility at lower pressures. Under conditions of complete miscibility, it was found that the length of the gas-solvent mixing zone could be predicted from the correlation developed for the solvent-oil mixing zone. With partial miscibility, two phases exist and the solvent is displaced by a modified gas drive in which vaporization and condensation occur. Equations are developed to predict the performance of this type of displacement. Two plans are suggested for application of miscible fluid displacement. one for miscible displacement of the solvent and the other applying to lower pressures where partial miscibility occurs during solvent displacement. Calculations based on the laboratory tests indicated that a bank of solvent with a volume of less than 10 per cent of the hydrocarbon volume under consideration will generally be adequate to obtain high oil recovery from the portion of the reservoir contacted in miscible fluid displacement. INTRODUCTION The conventional methods by which oil is displaced from reservoir rock—solution gas drive, conventional gas drive, and waterflooding—are all processes in which the oil is expelled from the rock by direct displacement with a fluid immiscible with the oil. Because of the immiscible type displacement, complete recovery of the reservoir oil is not achieved. In economically successful flooding operations, as much as 50 per cent of the original oil may be abandoned in the reservoir as unrecoverable. The use of a solvent (miscible with oil, such as LPG) as an injection fluid does not have the undesirable displacement features common to the use of gas or water (immiscible with oil). It can be readily appreciated, however, that it would not be economically feasible to displace the oil and entirely replace it with a solvent. A process was therefore devised for use in field operations in which only a small volume of solvent would be required to obtain essentially complete oil recovery in the portion of the reservoir contacted. In this process, the solvent acts as a buffer between the reservoir oil and injected gas, allowing the natural gas to displace indirectly the oil with much greater efficiency than if the gas displaced the oil directly. DESCRIPTION OF OIL RECOVERY PROCESS The solvent oil recovery process will be described in

Jan 1, 1958

By R. S. Schechter, T. R. Guilinger, P. Bobeck, J. G. Price, L. W. Lake

This paper presents the results of an experimental study on the rate of uranium and molybdenum extraction from a flow reactor. Specific variables tested are fluid throughput and flow rate, lixiviant cation, and injected pH and carbonate concentration. The ore tested was from the Felder mine in southern Texas. It contained substantial quantities of marcasite and molybdenum disulfide that competed with the uranium ore for oxidant. Flow studies showed the oxidation of molybdenum disulfide under field conditions is mass transfer controlled, whereas the uranium oxidation is limited by surface reaction rate. The rate of uranium oxidation decreased with decreasing pH. The total carbonate levels, on the other hand, were unimportant. Ammonium carbonate appears to greatly decrease, if not completely halt, the reaction of marcasite with the oxygen. This effect was not found using either sodium or potassium carbonate.

Jan 1, 1986

By E. A. Anderson, C. W. Siller, Gerald Edmunds

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940

By Gerald Edmunds, C. W. Siller, E. A. Anderson

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940

By Arthur C. Forsyth, R. L. Dowdell

A search through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1. Experimental Procedure The alloys were prepared from metals of commercial purity, as follows: electrolytic nickel 99.60 + 0.35 Co; chemically purified silicon 99.79 per cent plus impurities of Fe 0.027, A1 0.008, Ca 0.014, C 0.004, N² 0.10; and cobalt 98.82 per cent plus impurities of Ni 0.42, Fe 0.12, CaO 0.27, S 0.012, Mn 0.10 and SiO² 0.15. It should be noted that the largest impurity in cobalt is nickel, one of the alloying elements. The alloys were melted in a small Ajax induction furnace, the nickel and cobalt being melted first because of their better ferromagnetic

Jan 1, 1940

By Arthur C. Forsyth, R. L. Dowdell

A search through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1. Experimental Procedure The alloys were prepared from metals of commercial purity, as follows: electrolytic nickel 99.60 + 0.35 Co; chemically purified silicon 99.79 per cent plus impurities of Fe 0.027, A1 0.008, Ca 0.014, C 0.004, N² 0.10; and cobalt 98.82 per cent plus impurities of Ni 0.42, Fe 0.12, CaO 0.27, S 0.012, Mn 0.10 and SiO² 0.15. It should be noted that the largest impurity in cobalt is nickel, one of the alloying elements. The alloys were melted in a small Ajax induction furnace, the nickel and cobalt being melted first because of their better ferromagnetic

Jan 1, 1940

By William E. Greenawalt

Ever since electrolytic copper refining gave promise of success, about a half century ago, efforts have been made to apply the idea to the extraction of copper from its ores. The methods of attack have, usually, been to leach with a dilute acid and then to deposit electrolytically the copper from the resulting solution with the simultaneous regeneration of the solvent used in the process. Many efforts have been made, and many patents have been taken out, both in the United States and abroad, to give this idea practical application, but only within the past few years have the difficulties been surmounted. Leaching and electrolysis, as applied to copper ores, are among the most promising fields in modern metallurgy. New conditions are arising, which will bring the wet methods into prominence; while high freight rates and increasing cost of fuel will tend to limit smelting to highly favored localities. The possibilities offered by the installation of hydroelectric plants and the greatly enlarged range of power transmission will greatly widen the field of electrolytic methods. Electrolytic methods are ideally adapted to hydroelectric development, for the load is constant throughout the full twenty-four hours, and the cost of both installation and operation of hydroelectric plants is not appreciably greater when operating for twenty-four hours than when operating for eight or ten hours; whereas, in fuel-power generation, as also in smelting, the cost is more or less in proportion to the fuel and power used. Nevertheless, fuel-power generation presents advantages in electrolytic methods, as the power plant may be located in a favorable place while the leaching and electrolytic plants may be located at the mine. The ultimate possibilities of the wet methods have yet to be determined. The possibilities of smelting have been thoroughly worked out; there is no unsolved major problem in copper smelting, and it has practically reached the limit of its possibilities. It seems hardly probable that any future improvement, either of method or apparatus, will greatly

Jan 1, 1924

By Ellis H. Gates

BENEFICIATION of the manganese oxide ores at Three Kids Mine near Henderson, Nev., has evolved over a period of years. Commercial application of the process is on a secure basis, and an effective working hypothesis has been formulated to help solve the problems encountered in flotation. An outstanding difference between the Manganese Inc. operation and other flotation processes is the necessity for high recovery of slime mineral values. Part of the manganese minerals in the Three Kids ore deposit occurs as primary slime or as minerals that are easily slimed by grinding. High recovery of this slime portion is essential to an economic overall manganese recovery. The aim of much of the research at Manganese Inc. was to recover these slimed and finely ground minerals by flotation. Early Agglomeration Processes: Tunbridge' in 1880, followed by Everson2 in 1886 and Cattermole" in 1904, discovered that under certain pulp conditions precious metals and sulfide minerals could be agglomerated if enough soap or oil were mixed into the pulp slurry. These agglomerated particles, Which under ideal conditions ranged from 1/16 to 1/4 in. diam, were recovered by screening, tabling, and hydraulic classification. Even flotation by air occluded in the agglomkrate particles by vigorous stirring was suggested. Cattermole nearly succeeded in getting his process into commercial operation, but it was finally abandoned, presumably because he could nat compete with the low reagent requirements of the new agitation froth process. Since Cattermole's time Christensen in 1921, Borcherdt4 in 1926, and Chapman and Littleford- in 1934 have attempted to apply the principles of agglomeration. In the light of current research at Manganese Inc. on conditioning of pulp at high energy input levels, it is interesting to note the variety of equipment such as tumbling mills, mixing drums, and shakers described by Borcherdt in his patent to produce the agglomerated particles. Ore Characteristics: Manganese in the Three Kids ore occurs as a 'complex mixture of manganese oxides commonly Known as wad. The manganese minerals have Been identified as psilorflelane, hollandite, coronadite, and pyrolusite with minor amdunts of rhodonite and rhodochrbsite. The ppincipal gangue miherals are quaktz, opal, kaolinite, montmoril-lonite, calcite, gypsum, fcelesitite, and barite. Most of the mangandse ore minerals are either porous and sponge-like in structure or soft clay-like masses composed of fine grained mineral particles approaching the size range of colloids. Consequently the ore minerals from the Three Kids mine have relatively large surface areas and high void content per unit weight. The specific area of various manganese ore samples measured at the California Research Corp. laboratories ranged from 32 to 58 sq m per g. The great surface area and high void content explains in part the unusually high reagent consumption required in the treatment of this ore. Current Milling Practice: At Henderson6 he ore is crushed to —1 in. and ground with rod mills in a closed circuit with spiral rake classifiers and cyclones. Sulfur dioxide solution is added to the pulp as it leaves the grinding circuit, immediately followed by addition of a reagent mixture of soap, oil, and wetting agent in the form of an emulsion. The reagents are initially well mixed into the pulp during their passage through centrifugal pumps to the conditioning equipment. All reagents are added prior to conditioning. The intense conditioning or mechanical stirring of the pulp, in which large amounts of power are consumed, is the principal difference between the flowsheet used at Manganese Inc. and a standard flotation circuit. As much as 38 kw-hr of energy per dry short ton of ore in a pulp containing 18 to 23 pct solids is used for conditioning. After conditioning, the pulp passes to a flotation circuit that consists of one roughing stage, a scav-

Jan 1, 1958

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By Harold Margolin, W. R. Hibbard, R. W. Fenn, H. P. Moore

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By E. J. Horwood

The varying physical character and large extent of the Broken Hill lode necesarily involve the employment of a variety of underground methods. The lode had its origin in an extensive fault plane traversing metamorphosed schists conformably, as a rule, with their beds of stratification. The underground waters carrying minerals in solution deposited their contents in the original cavities formed by the faulting action, and in the enlargements of these cavities due to dynamic forces brought to bear on the rocks, more especially on the hanging-wall side of the fault. This deposition was supplemented by metasomatic replacement of a portion of the original rock contents by the argentiferous sulphides of lead and zinc which form the staple products of the district. Although the orebody is practically continuous throughout the mines, its width varies greatly, ranging from a few feet to about 350 ft. The widest portions occur in conjunction with huge folds in the inclosing country rock, almost exclusively on the hanging-wall side. The ore in these folds pitches to the south in the southern half of the field, and to the north in the northern half; there are, however, undulations in these ore channels evidently due to compression of the rocks in the direction of the channels. In the earlier days, before the orebodies had been opened up, vertical cross-sections across these bulges in the hanging wall gave the lode the appearance of the "saddle formation," so well exemplified at Bendigo in Victoria; but subsequent development of the ore channels has long since proved that the formations in the two districts are entirely different. The depth reached by the zone of complete oxidation of the sulphides varies from about 259 to 550 ft, from the original outcrop, while partial oxidation extends in places below the 1,000-ft. level. The result of oxidizing influences has been the production of ore of every grade of cohesive-ness, from that of dry sand to that of hard compact rock. The methods of mining followed in this field, and even in individual mines, are varied in accordance with the character of the ore. The general practice of the field is to sink vertical shafts, generally on the foot-

Jan 1, 1916

By M. H. Gaskell, D. C. Lindley

Small, steeply inclined reservoirs without natural water drives often are found associated with salt domes or other highly faulted structures. Frequently, only one well may be economically justified in these reservoirs, from which oil is produced by an expanding gas-cap drive or by a dissolved-gas drive. Although a large fraction of the oil upstructure from the well may be recovered during primary depletion, only a small fraction of the downdip oil can be produced because of gravity effects. This downdip oil has been defined as cellar oil991 in contradistinction to "attic oil" which is the oil above the structurally highest well in reservoirs where a natural water drive is present. In this study, two methods of producing cellar oil by water flooding a one-well reservoir were investigated by means of a laboratory model. This model was scaled to represent a prototype reservoir having an area of 30 acres, a permeability of 500 md, and a thickness and dip of 30 ft and 30°, respectively. One method considered, the simultaneous injection of water and production of oil from a single well, would require that the lower portion of the productive interval of a well be completed for water injection and the upper portion for oil production. The other method considered, intermittent injection, would involve alternate injection of water into and production of oil from a single well. Injection of water into the formation would repressure the reservoir, causing gas to go back into solution. Since some of the injected water would flow updip from the well, water injection usually would be followed by a waiting period during which the water could drain from above the wellbore. Production of oil by gravity drainage and gas-cap drive could be initiated when water drainage became sufficiently complete. The amount of water produced along with the oil would naturally depend on how soon after water injection ceased that production was started. This process could be repeated in cycles until oil could no longer be produced economically. Of these two methods, the intermittent injection technique would be simpler to put into operation since it does not require a dual completion. Also, it is probably more generally applicable than the simultaneous injection-production method. It is to be expected that in some reservoirs the rock and fluid properties would be such that practical oil-production rates could not be achieved by the simultaneous technique. However, in reservoirs where the simultaneous method will result in practical rates of oil production, it does have the advantage of permitting immediate, continuous oil production; whereas in the intermittent method, oil production is interrupted by periods of water injection and drainage. It was the objective of this study to determine whether these two methods of cellar oil production are practical for the representative prototype investigated and to evaluate their relative merits. DESIGN OF LABORATORY MODEL SCALING REQUIREMENTS The prototype reservoir and fluids were selected to have the dimensions and physical properties shown in Table 1. The laboratory model was then designed in accordance with well known scaling criteria, as discussed by Croes, et al,2 except for one modification. According to Croes, et al, one requirement of scaling a laboratory model to a reservoir prototype is that both the relative permeabilities and dimensionless capillary pressure be the same functions of water saturation for the model and the prototype. Since unconsolidated sand packs are used in the laboratory model to represent the consolidated porous media of the prototype, it is virtually impossible to satisfy this requirement. Much of the difficulty stems from the fact that unconsolidated sands usually exhibit lower residual oil and connate-water saturations than do reservoir rocks. To satisfy the scaling requirement as nearly as possible, Perkins and Collins' have suggested that the relative permeabilities be re-defined as

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By M. C. Leverett, M. E. True, W. B. Lewis

This paper states the theory underlying the design of two kinds of dimensionally scaled models of parts of idealized oil fields. One of these simulates an oil well and its surrounding sand for a distance of 16 ft. radially from the well. The other model simulates linear flow through layered sands. Construction and operation of the models are described and typical data are given. The unique features in the design of the models are: (I) the treatment of the permeability-viscosity quotient as a single variable and (2) the use of previously reported experimentally developed relations between relative permeability and saturation and capillary pressure, saturation, porosity, permeability and interfacial tension. The models at present simulate flow of oil and water only, through unconsolidated sands. They are superior to unscaled models, which may give rise to erroneous conclusions. The models are designed to study the desirability of various methods of well completion and the effects of various factors on recovery of oil from layered sands. Introduction Recent work on the fundamental behavior of flowing mixtures of fluids in sands has resulted in the development of some new theory in this field, much of which has been presented in previous papers.l-4 However, the application of this theory to the behavior of oil wells or oil fields has proved too complicated for ordinary mathematical techniques, except in very highly simplified cases. A practical solution to this problem appears therefore, to lie in the use of dimensionally scaled models of elements of oil fields. The object of this paper is, first, to present the theoretical and experimental basis of the design of such models, and, second, to describe their construction and operation. Experiments now under way on the models already built will yield material for other reports, which will be devoted to interpretation of the results in terms of oil-field behavior. So far, simple dimensional models of two kinds have been built and are being operated. These models represent different parts of an idealized oil field but obey the same underlying theory. The only fluids represented are oil and water, since certain questionable approximations are necessary for gas-liquid systems. General Theory Dimensional models have been used in other fields for a long time, and their theory is adequately given in the literature. 5 Here, it suffices to state that each physical element entering into a dynamic relation may be given a definite description in terms of three fundamental, but arbitrarily chosen, dimensions. These usually are mass, length, and time, symbolized here by the small letters m, I, and t. Two systems are said to be dimensionally similar or dimensionally scaled if for each element in one system there is a corresponding element in the second system and the ratios of the numerical magnitudes of corresponding elements are constant for all elements of the same dimensional type.

Jan 1, 1942

By W. B. Lewis, M. E. True, M. C. Leverett

This paper states the theory underlying the design of two kinds of dimensionally scaled models of parts of idealized oil fields. One of these simulates an oil well and its surrounding sand for a distance of 16 ft. radially from the well. The other model simulates linear flow through layered sands. Construction and operation of the models are described and typical data are given. The unique features in the design of the models are: (I) the treatment of the permeability-viscosity quotient as a single variable and (2) the use of previously reported experimentally developed relations between relative permeability and saturation and capillary pressure, saturation, porosity, permeability and interfacial tension. The models at present simulate flow of oil and water only, through unconsolidated sands. They are superior to unscaled models, which may give rise to erroneous conclusions. The models are designed to study the desirability of various methods of well completion and the effects of various factors on recovery of oil from layered sands. Introduction Recent work on the fundamental behavior of flowing mixtures of fluids in sands has resulted in the development of some new theory in this field, much of which has been presented in previous papers.l-4 However, the application of this theory to the behavior of oil wells or oil fields has proved too complicated for ordinary mathematical techniques, except in very highly simplified cases. A practical solution to this problem appears therefore, to lie in the use of dimensionally scaled models of elements of oil fields. The object of this paper is, first, to present the theoretical and experimental basis of the design of such models, and, second, to describe their construction and operation. Experiments now under way on the models already built will yield material for other reports, which will be devoted to interpretation of the results in terms of oil-field behavior. So far, simple dimensional models of two kinds have been built and are being operated. These models represent different parts of an idealized oil field but obey the same underlying theory. The only fluids represented are oil and water, since certain questionable approximations are necessary for gas-liquid systems. General Theory Dimensional models have been used in other fields for a long time, and their theory is adequately given in the literature. 5 Here, it suffices to state that each physical element entering into a dynamic relation may be given a definite description in terms of three fundamental, but arbitrarily chosen, dimensions. These usually are mass, length, and time, symbolized here by the small letters m, I, and t. Two systems are said to be dimensionally similar or dimensionally scaled if for each element in one system there is a corresponding element in the second system and the ratios of the numerical magnitudes of corresponding elements are constant for all elements of the same dimensional type.

Jan 1, 1942

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, 'so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950

By AIME AIME

THE joint symposium on gases in metals on Tuesday: Feb. 16, between the Iron and Steel and the Institute of Metals divisions opened the technical sessions for both of these bodies. After a few words of introduction by P. D. Merica, R. S. Dean presented a paper by V. H: Gottshalk and himself on the solubility of gases in metals.

Jan 1, 1932

By Wm Price

THE object of this paper is to present a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350° C. throughout the commercial annealing range. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: ALLOY COPPER, LEAD, IRON, NICKEL, MANGANESE, ZINC, PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. PER CENT A 64.68 Trace 0.194 - 6.73 0.06 remainder B 65.82 1.27 0.227 6.17 0.06 remainder C 65.44 Trace 0.345 17.83 0.08 remainder D 65.60 1.08 0.238 17.77 0.06 remainder These alloys were rolled in accordance with regular mill practice to approximately No. 6 B. & S. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately .one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 ½ in. long by ;Z in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 2 1/2 in. were also taken.

Jan 10, 1920