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By M. G. Jones

AT the Edwards mine a 4 by 81/2-ft two-compartment shaft is used for men and supplies in the older workings down to the 900-ft level. All ore is hoisted through a 5 by 15-ft three-compartment vertical shaft which extends to the 1500-ft level. Ore pockets are on the 1300- and 1500-ft levels. The two-compartment countershaft used below the latter level is 6 by 12 ft inclined at 42°. Ore from the countershaft is hoisted to the 1350-ft level where it flows by gravity to the 1500-ft level ore pocket. One-ton skips are used in balance in the countershaft and two-ton skips, also in balance, from the 1500-It level to the surface. These skips are slung under the man cages. Each level has an ore pocket of 200 tons' capacity. Development at Edwards is similar to that at Balmat except that haulage drifts are only 7 by 7 ft. They are mucked with Eimco-Finlay No. 12 loaders. A drill carriage similar to that used at Balmat is being tried out on the new 2300-ft level, the present bottom of the mine. Drifts are driven below grade and later raised 6 in. and ballasted with waste leaving a ditch 6 by 12 in. at one side for drainage. All development is done on an incentive bonus system, the miner paying for his explosives.

Jan 1, 1947

By AIME AIME

APROXIMATELY one third of the world's iron ore is mined in the United States; and about 80 per cent of this third is mined in the Lake Superior ore region, and about 60 per cent in Minnesota. The Lake Superior iron ore region covers a vast area in the vicinity of Lake Superior that contained in early geological times large areas of iron-bearing sediments, which today form metamorphosed iron-bearing rocks, such as jasper, chert, taconite, and slates. Concentration of the iron content chiefly through solution and resultant removal of silica produced the ore bodies we find today in rock folds as on the Menominee range, at dike or impervious wall intersections such as on the Gogebic range, and blanket-type enriched ore bodies ly¬ing on or within the ore formation, such as occur on the Mesabi and in steeply pitching ore lenses elsewhere. In many places, folding and subsequent erosion of the tops of the folded areas has resulted in steep dips in the ore formation and contained ore bodies. The upper eroded edges are mostly buried under glacial over-burden. The slightly dipping Mesabi formation is the principal exception as to steeply dipping ore bodies.

Jan 1, 1941

By Robert S. Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultirnatc cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of .the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development. The alloys or processes to be used in the production of aluminum castings are to be considered from the standpoint of their effects on both the utility and the cost of the finished casting. Specific gravity and mechanical properties come under the first head, while the properties

Jan 1, 1927

By V. L., McCutchan

FORM of ore bodies, strength of wall rock, and quantity of water that must be handled differ so greatly in the various districts in which the Corporation operates that a variety of mining methods have to be employed. All are underground, however, with the exception of glory holes at Cerro de Pasco from which siliceous silver pacos ore is obtained. In general, the ors is in many relatively small bodies unsuitable for hulk mining, such as caving or top slicing. The strength of the rock and ore rarely permit open stopes, though shrinkage is successfully used on various veins with strong walls, particularly in, Casapalca. Horizontal cut and-fill and square-set stoping with careful filling are the principal methods employed, with the necessarily higher cost for supplies and labor offset as much as possible by care in the avoidance of dilution. The mines at both Morococha and Casapalca are notoriously wet, and even at Cerro de Pasco the quantity of water was enough to retard deep development until the perfection of electric pumps. In Morococha particularly, the extension of successive levels, first from adits of moderate length, then from shafts and heavy pumping installations on the 750 and 1000 levels, and finally by the 30,564-ft. Kingsmill tunnel, was one of the most difficult and long continued fights against water and resulting heavy ground that is recorded in mining history.

Jan 1, 1945

By W. S. Morris

PETROLEUM'S importance in World War II can perhaps be better realized by the recitation of a few facts and figures: Gasoline needs in this war are already eighty times greater than in the last war. It takes nearly three pounds of gasoline to deliver one pound of bombs, filled with petroleum explosives, on an enemy objective. Every American soldier overseas requires an average of more than fifty gallons of petroleum products per week, with the oil used by Navy and supply ships and America's Allies boosting the consumption of oil per soldier to an even higher figure. Every oil well in the United States now must produce each day an average of four barrels of oil for war and combat jobs. More than fifty million gallons of gasoline, fuel oils, lubricants, and other petroleum products are now going directly to the fighting forces every day.

Jan 1, 1945

By John H. Schilling

The Gabbs magnesite-brucite deposit is unique in size and is one of two magnesite deposits being exploited in the United States. It is near the town of Gabbs, which is one hundred miles southeast of Reno, in west-central Nevada. The brucite was discovered in 1927; the magnesite was found while exploring the brucite. During World War II, more than 80,000 tons of magnesium metal was produced from about 900,000 tons of magnesite ore mined from these deposits. An additional 5,000,000 tons of magnesite and 1,000,000 tons of brucite have been produced for use in making magnesia refractories and chemicals. Basic Inc., presently the only producer, mines 1.5 ± 0.25 million tons of ore and waste annually using high-selective open-pit rriethods; the ore is up-graded, calcined, and processed into a variety of products. Known reserves of highgrade (less than 5 per cent CaO) magnesite ore total more than 25,000,000 tons, and there are larger tonnages of lower-grade material; brucite reserves are small. The magnesite and brucite are in generally west-dipping dolomite of the upper member of the late Triassic Luning Formation, in the over-riding plate of the Paradise thrust fault. A great variety of dikes and a stock of Cretaceous granodiorite intrude the Luning Formation in the vicinity of the magnesite-brucite deposit. The magnesite bodies are scattered over an area of about a square mile around a prong of granodiorite which extends north from the stock. The brucite is mainly in two bodies in contact with the prong of granodiorite; at the surface and along deeper cracks the brucite has weathered to hydromagnesite and artinite. In the area of magnesite-brucite mineralization, much of the dark, fine-grained, schistose, regionally-metamorphosed dolomite of the Luning Formation has been marmorized to a lighter-colored, coarser-grained, massive dolomite that is intergrown in varying proportions with the magnesite. The magnesite and marmorized dolomite can not be distinguished visually. In addition to the two varieties of dolomite, the gangue in the magnesite and brucite bodies mainly is the various varieties of dike rock, serpentine and a variety of other "contact" minerals, and "post-ore" dolomite and calcite. The magnesite ( and recrystallized dolomite) is believed to have formed by the hydrothermal replacement of the regionally metamorphosed sedimentary dolomite; alternatively it has been suggested that the magnesite is sedimentarv and formed contemporaneously with the dolomite in an embayment of the Triassic sea. Because all the igneous rocks exposed in the immediate vicinity of the magnesite deposits appear to be younger than the magnesite, the ore-forming solutions are thought to be related to a somewhat older granite which crops out elsewhere in the area. The brucite is the result of contact-metasomatic replacement of magnesite during the emplacement of the granodiorite stock.

Jan 1, 1968

By J. B. Dilworth

I. INTRODUCTION. THE purpose of this paper is, first, to give a general account of a little-known coal-district of SE. Kentucky, its topography, drainage, and mineral resources, for those who may be interested in its economic development; and secondly, so to describe the geologic features of the field as to furnish available data to those engaged on the broader problems of Appalachian coal-geology. The data from which the major portion of the paper has been prepared were obtained, in professional investigations for private individuals and corporations, within the last decade. The area under review, defined by a heavy line on the map, Fig. 1, lies between Little Black and Pine mountains, and extends from Harlan on the west to a N-S. line crossing Looney creek 3 miles from its mouth on the east. This area can be divided for description into a Western and an Eastern Division. The character of investigation pursued in the Western Division, below Fugitt creek, was very different from that employed in the Eastern. In the former, only a rapid reconnoissance was attempted : such coal-openings as had been made by prospectors or by citizens in obtaining fuel were visited, their sections measured and, in many instances, sampled. Elevations were obtained barometrically and approximate locations sketched on a small-scale map. In a field where the coals are so well opened, the reconnoissance method gives a very fair idea of the number and character of the principal beds and their relative positions, and affords much evidence for their correlation over wide areas, without permitting the more refined work required to discover all the seams of the measures and to determine the details of geologic structure.

Feb 1, 1912

Jan 1, 1929

By N. O. Taylor

THE failure, by swelling, of several cast aluminum-zinc, spiral, pump rods, used to circulate water in a constant-temperature bath, brought up the question as to whether the presence of tin in varying quantities would have any appreciable influence in controlling this action. Previous workers had found the same difficulty with aluminum-zinc alloys, due to their swelling in water or solutions of electrolyte^.^ It was known that pure aluminum was practically insoluble in concentrated sulfuric and nitric acids, presumably due to the formation of an oxidized film on the surface. Concentrated sulfuric acid had little or no effect on pure zinc and tin and concentrated hydrochloric acid would attack all three metals. These facts aroused curiosity as to the probable reaction of the ternary alloys of these metals, and tests were made to determine their resistivity to the action of common laboratory reagents. Samples, covering the entire range of the ternary series of aluminum, zinc and tin alloys, were made up from good grades of the commercial metals.2 The materials were melted, at as low temperatures as possible, in graphite crucibles in a gas-fired crucible furnace. Graphite crucibles were used in preference to clay, to prevent the absorption of silicon by the aluminum, as found by previous workers. The melted materials were stirred thoroughly with pine sticks in order to ensure complete mixing and the greatest possible freedom from oxidation, and were cast in sectional, iron molds giving bars % in. in diameter and 5 in. long.

Jan 1, 1927

By John A. Emery

The Pea Ridge iron ore deposit near Sullivan, Missouri, is a dike-like mass of magnetite enclosed in Precambrian porphyries. The ore body tops at the Precambrian surface at a depth of 1300 feet below the present surface and extends to an unknown depth. It dips nearly vertically, intersecting the dip and strike of the enclosing porphyries at an extremely sharp angle. Faulting, both pre- and post-ore, appears to be of minor consequence, and present knowledge indicates that no preferred structural conditions existed prior to emplacement. The ore body is composed of magnetite with specular hematite, quartz, apatite, and pyrite occurring as accessory primary minerals. Specular hematite in appreciable quantities occurs on parts of the cap and the footwall of the ore body. Fresh porphyry breccia is enclosed in the magnetite along the hanging wall and in the western portion of the ore body. Hanging-wall quartz-amphibole and footwall quartz-hematite occur as replacements of certain porphyries. Further alteration has caused sericitization of parts of these zones. The ore deposit is interpreted as having been formed essentially by a single injection of a magmatic differentiate with hydrothermal end phases forming the quartz-amphibole and quartz-hematite portions of the deposit.

Jan 1, 1968

By W. A. STERLING

IN the opencut iron mines of the Mesabi Range in Minnesota, the trend in mining is in the development of mining equipment and mining methods which will move surface overburden and ore-bearing materials with less labor and at a cheaper cost. This is a must for most of the independent operators. Their reserves of direct-shipping ore are extremely small and their operations are being conducted in small, or intermediate pits, with a high stripping ratio in the outer fringes, or shore lines of older pits. and in ore bodies passing from direct shipping to the washing and the intermediate, or retreat ore state. The trend is toward deeper stripping, longer and steeper hauls, and the necessity of moving a total of from three to five or six tons of overburden and ore material for each ton of shipping-grade ore produced. This naturally calls for greater production, with larger shovels, or draglines. cheaper drilling and blasting costs through the drilling of larger-diameter blastholes, and cheaper haulage through the use of trucks of larger capacity and more extensive use of belt-conveyor systems. This trend is notable both in stripping and mining.

Jan 1, 1948

By J. J. Fritts, J. L. Patrick, T. L. Wright, C. O. Ensign, W. S. White, J. W. Trammell, J. C. Wright, D. J. Hathaway, R. J. Leone

The copper deposit at White Pine, Michigan, from which a little more than 5 per cent of United States primary copper currently is produced, is a large stratiform orebody, 4 to 25 feet thick and several miles across. The present ore column, containing about 1.2 per cent copper as chalcocite and native copper, is confined to the basal beds of the Nonesuch Shale. This upper Keweenawan (Upper Precambrian) formation is a distinctive gray siltstone unit, about 600 feet thick, overlying and overlain by thick red-bed sequences. All these rocks contain abundant volcanic debris, but the latest known igneous activity within 50 miles antedated the Nonesuch Shale. The rocks are unmetamorphosed and only moderately deformed, mainly by tilting and faults. Pyrite, presumably syngenetic, is the only prominent sulfide throughout most of the Nonesuch Shale. The basal beds of the formation, however, contain disseminated copper minerals instead of pyrite and constitute the cupriferous zone. On a regional scale, the top of the cupriferous zone cuts across bedding, and ranges from an inch or so above the base of the formation in some areas to more than 50 feet in others. However, within the cupriferous zone the distribution of copper shows remarkable stratigraphic control. Certain beds are copper-rich compared to the beds that lie between them and the differences persist throughout the White Pine region. Several darkgray thinly laminated beds in the lower 10 to 25 feet of the Nonesuch Shale are rich enough and sufficiently close enough together to constitute a mineable thickness where they lie within the cupriferous zone. Pyrite is the characteristic sulfide of the Nonesuch Shale as a whole. The principal sulfide mineral of the cupriferous zone at the base of the formation is chalcocite. The succession of minerals outward and upward from the center of the cupriferous zone is native copper-chalcocite-bornite-chalcopyrite- pyrite. The bornite and chalcopyrite are confined to a narrow fringe at the margin of the cupriferous zone. This pattern of mineral zones is believed to represent reaction between syngenetic pyrite and introduced copper. The main copper mineralization is independent of structure and apparently antedates deformation. Details of the geometry of the cupriferous zone indicate the possibility that copper was introduced from the underlying sandstone prior to lithification. The source of the mineralizing solutions and their copper is not known.

Jan 1, 1968

By John T. Eastlick

The Banner mining district is about 70 miles northeast of Tucson in the southern part of Gila County, Arizona. Production from the district, valued at about $26 million, is chiefly from copper-silver-lead zinc ores. The stratigraphic section consists of Precambrian conglomerates, quartzites, dolomites, and limestones, Cambrian quartzites; Devonian limestones; dolomites, and shales; Mississippian limestones; Pennsylvanian limestones and shales; and Cretaceous volcanic and sedimentary rocks. Deformation of these rocks presumably started near the end of the Cretaceous, and extended into the late Tertiary. The sedimentary rocks were folded, faulted, and intruded by fine grained diorite, quartz mica diorite, and dacite porphyry. At least four distinct stages of mineralization are recognized. In the first stage of contact metamorphism and the second stage of hydrothermal alteration, favorable zones were prepared for ore deposition. Metallization occurred in three of the mineralizing stages. Magnetite, pyrite, and hematite were deposited near the end of the second stage of hydrothermal alteration. The third stage included the main deposition of sphalerite, chalcopyrite, bornite, and galena. In the fourth and final stage, minor amounts of sulfide minerals were deposited with a late anhydrite and quartz gangue. The ore deposits in the form of veins and veinlets, pipes, irregular massive replacements, and bedded replacements are localized by the extent and distribution of metamorphic and hydrothermal alteration, by the proximity to the intrusive contacts, and by the effects of structural development. Oxidized ores of copper, lead, and zinc constituted the principal production of the district prior to 1940, but, for the most part, supergene enrichment was of minor economic importance. The ore bodies of the district are in the mesothermal class of deposits, occurring as normal metasomatic replacement and vein types.

Jan 1, 1968

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By G. W. Tracy, R. D. Carter

Numerical calculations were made to determine the behavior of reservoirs with high-pressure drawdown and wide well spacing where the initial productivity is low and the wells are completed by hydraulic fracturing. The two-phase flow equations were solved for the flow into a single well. This well was assumed to be producing from a reservoir with hydraulically created horizontal fractures (four different systems with fractures were studied). For comparison purposes, additional two-phase flow calculations were made assuming a reservoir with uniform rock properties. The two-phase flow results were also compared with the conventional calculation methods, which do not include the effect of saturation gradients resulting from a simultaneous flow of oil and gas which are normal to this type reservoir. It was found that the conventional methods predict (1) a high and too optimistic value of ultimate recovery, (2) a high producing rate and a high reservoir pressure at a given oil recovery and (3) a low trend of gas-oil ratio with oil recovery. Included in the two-phase flow calculations were provisions to control the oil production rate by an allowable rate and, also, by a gas-oil ratio penalty rule. For the systems with hydraulic fractures, the producing rate was controlled by the gas-oil ratio penalty rule for most of the life. This is in contrast to the system with uniform rock properties which went "on decline" almost immediately. An unexpected characteristic of the systems which included fractures was the early rise in producing gas-oil ratio from 730 cu ft/bbl to approximately 1,200 cu ft/bbl, followed by a "leveling off" before the normally expected gas-oil ratio rise began. Additional features which are a result of hydraulic fracturing are (I) greater ultimate recovery, (2) higher average producing rates and (3) a lower average reservoir pressure at a given oil recovery. INTRODUCTION Some oil fields discovered during the past few years are producing from certain volumetric ally controlled reservoirs (often referred to as solution or internal gas- drive reservoirs) which are characterized by high-pressure drawdown at the wells. Since the available pressure drawdown at a well is limited by the static reservoir pressure and the producing rate is controlled by the available drawdown, wells completed in this type of reservoir usually produce at a rate less than the allowable from the time of completion. Because of this, this type of reservoir is referred to as a low productivity reservoir. Economic considerations require the use of wide well spacing and well stimulation by hydraulic fracturing to make commercial wells in this type of reservoir. Performance predictions for volumetrically controlled reservoirs have been made using a combination of two standard equations. 1. The "Schilthuis" or "Muskat" type material balance equation is used to relate the average reservoir pressure and the cumulative oil recovery. 2. The results from the material balance equation and the productivity factor as described by Pirson' are used to relate the cumulative recovery with producing rate and time. The material balance equation assumed uniform pressure and liquid saturation conditions throughout a reservoir. The steady-state radial flow formula allows for a pressure gradient toward a well but assumes uniform liquid saturation. These calculation methods are adequate for application to reservoirs wherein the drawdown at the well to realize satisfactory producing rates is small compared to the total pressure. In low productivity, volumetrically controlled reservoirs, the pressure drawdown at the well is large cornpared to the total pressure. Although a precise number cannot be given for the magnitude of a large pressure drawdown, values in excess of 1,000 psi would definitely be included. For practical considerations, this usually occurs when the formation flow capacity is less than about 100 md-ft. However, this limit of formation flow capacity will vary with the well producing rate. The low pressure in the neighborhood of the well which results from a high drawdown causes evolution of large volumes of gas. This causes the gas saturation to be higher near the well than at a greater distance—-hence, a non-uniform gas saturation. Also, the relationship between the relative permeability to oil (K/K) and gas saturation is nonlinear but decreases approximately in an exponential way with increases in gas saturation. Because of this, the following chain reaction is established.

By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965