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By Holbrook G. Botset

Experiments performed in this laboratory on the flow of gas-liquid mixtures through unconsolidated sands have been described and discussed in an earlier paper.4 In these earlier experiments a definite relationship was found between the liquid saturation of a sand and its permeability to the liquid or gas phase. Furthermore, the nature of the sand, the permeabilities of the sands over a range between 17 and 260 darcies, appeared to have a negligible effect upon the saturation-permeability relation. Likewise experiments indicated that the viscosity of the liquid, or the substitution of an immiscible liquid for the gas phase, had only a very slight effect on the permeability-saturation relation. This conclusion has since been definitely confirmed by the experiments of M. C. Leverett3 on the flow of oil and water through unconsolidated sands. The sands used by Leverett were of very low permeability (between 6.8 and 1.04 darcies), while the oil-water viscosity ratio varied between 90 and 0.057. Since the sands that constitute petroleum reservoirs are largely consolidated, although of widely varying degrees of consolidation, it was desirable to extend the experiments on gas-liquid mixtures to consolidated sand. In the study of consolidated sands additional variables are involved, but for the initial experiments the only new variable to be introduced was the cementing material. Experimental Procedure A comparatively limited assortment of sandstones was available for the selection of the experimental material. Of these, the Nichols buff sandstone appeared to be most suitable. It gives no visual evidence of any bedding planes, it has a firm structure, permitting easy handling, and its permeability is about 0.5 darcy. Its only disadvantage is the fact that it contains an appreciable amount of ferric oxide which, for experiments involving water, will hydrate and reduce the permeability. This

Jan 1, 1940

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct ThO2,*, and the ilmenite 56 1/2 pct TiO2, whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be avail- able in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources. 1 Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations.

Jan 6, 1950

By C. P. Parsons

Caliper logging is a practice of measuring the variations in the diameter of the open hole in a well. This information is useful for many purposes, among which are: Determining the volumetric capacity of the portion of open hole to be cemented; the amount of gravel to be used for gravel-packing a well; the size and location of seat for a packer to be placed in a well; studying the effects of nitroglycerin shots; studying the effects of acidizing; studying the cause of drill-pipe failures; studying drilling technique; geological correlations. This is a new practice in oil fields and is eliminating considerable guesswork. Introduction Caliper logging of the open hole in oil wells, recently introduced and now showing initial results in many sections of the country, is providing information that is filling a long-felt need in oil-well cementing and in numerous other oil-field practices. Briefly, it measures the variations in diameter, of the open hole in a well. This direct physical measurement of the strati-graphic profile has considerable value for subsurface interpretations by the geologist, engineer, driller and others charged with the responsibility of properly completing and repairing oil and gas wells. The caliper shown in Fig. I is run into a well in closed position. The four arms are released when logging is to start. These arms are independent of each other. As the calipers are pulled upward through the open hole, the arms are like nimble fingers feeling the changing profile of the hole. This mechanical action is in turn converted into an electrical circuit, which is connected to a recording mechanism at the surface. a. Lowered into well in closed position. b. Arms released. Readings are made while caliper travels upward. Direct recording is made at surface, in inches. The recording of the diameter of the hole is directly in inches.

Jan 1, 1943

By C. P. Parsons

Caliper logging is a practice of measuring the variations in the diameter of the open hole in a well. This information is useful for many purposes, among which are: Determining the volumetric capacity of the portion of open hole to be cemented; the amount of gravel to be used for gravel-packing a well; the size and location of seat for a packer to be placed in a well; studying the effects of nitroglycerin shots; studying the effects of acidizing; studying the cause of drill-pipe failures; studying drilling technique; geological correlations. This is a new practice in oil fields and is eliminating considerable guesswork. Introduction Caliper logging of the open hole in oil wells, recently introduced and now showing initial results in many sections of the country, is providing information that is filling a long-felt need in oil-well cementing and in numerous other oil-field practices. Briefly, it measures the variations in diameter, of the open hole in a well. This direct physical measurement of the strati-graphic profile has considerable value for subsurface interpretations by the geologist, engineer, driller and others charged with the responsibility of properly completing and repairing oil and gas wells. The caliper shown in Fig. I is run into a well in closed position. The four arms are released when logging is to start. These arms are independent of each other. As the calipers are pulled upward through the open hole, the arms are like nimble fingers feeling the changing profile of the hole. This mechanical action is in turn converted into an electrical circuit, which is connected to a recording mechanism at the surface. a. Lowered into well in closed position. b. Arms released. Readings are made while caliper travels upward. Direct recording is made at surface, in inches. The recording of the diameter of the hole is directly in inches.

Jan 1, 1943

By S. Parker Gay

In 1967 Southern. Peru Copper Corp. was faced with the problem of developing a water supply for their new Cuajone open-pit copper mining and milling operation, at a time when the existing water system was inadequate for a proposed expansion of the producing Toquepala mine. The most probable source for additional water was considered to be the Pasto Grande basin lying 30 km north of the terminus of the pipeline. This source of supply could be developed only at substantial cost, after construction of a dam, tunnels, pumping plants, and several miles of canals. Investigation of other possible sources was undertaken, and one of these was the Huaitire alluvial fan which had been recognized on aerial photographs in 1961. Resistivity soundings on the fan provided isopach information for estimating the volume of fan sediments. In the course of carrying out these soundings, a high-resistivity layer at depth was indicated. The favored geological interpretation of this layer at the time was a tight impermeable volcanic formation, but an alternative explanation was a ground-water aquifer of high transmissibility. Geological studies just released by the Peruvian Geological Map Commission supported the latter interpretation. A diamond drill hole sunk to a depth of 725 ft on the Huaitire Pampa in June 1967 proved the absence of the expected volcanics, the presence of the sediments, and indicated that some sedimentary horizons carried artesian water. Subsequent well drilling and hydrological and geological studies show that the aquifer occurs principally in the Upper Tertiary Capillune formation, covers an extensive area on the Peruvian altiplano, discharges enormous quantities of water to a large number of canyons dissecting it, and will adequately supply most, if not all, water needs of the Cuajone operations.

Jan 1, 1973

To the members of the A. I. M. E., who have given much and risked all to fight "Over There" with pick, or gun, or brain, and to the members who have chosen the sometimes more self-denying duty of remaining at home to help produce metals for fighters: Your experience in foreign lands has bred in you that spirit of internationalism which will soon be infused into every corner of our country by virile lads thrilling from a great experience in an old, yet new, land over the seas. To them the East will not seem as far from the West as it was, nor the North from the South. Sectional jealousies will seen despicable to one who has fought for a great ideal shoulder to shoulder with real men of other nations. And they who have willingly sacrificed much on the altar of service will have little patience with an egotist, be he laborer, tradesman, capitalist or engineer. The problems which peace brings to us are more difficult than those of war and their solution requires not only cool heads, tolerance, and wise judgment, but the "getting together" of sections and classes and individuals. The triumph of justice over individualism, represented by the draft law, must be repeated, for there are "slackers" in peace Is well as in war, and the spirit of self-denial expressed in response to Liberty Loans, Red Cross, and Welfare drives and Food Administration appeals must live. We have only just begun to learn how to serve. It is often claimed by our members that the engineer is not given, in the community at large, the recognition which his training should merit; that his reward is not as great nor his service as welcome as it should be. Public service is generally assumed to be a logical activity for a lawyer,

Jan 12, 1918

By W. M. Weigel

THE rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago, have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used, in its natural state after mechanical preparation only (such as. grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the eastern and northern states. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The southern states have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the north, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business. revives and freight rates are adjusted.

Jan 2, 1922

By Howard S. Bryant

The year 1928 has recently.passed from the picture and it is at this time that the various divisions of the oil industry are giving thought to plans for the present year. The outstanding characteristic of the industry in 1928 was the successful curtailment of oil production to the market's needs. It has been thought advisable to look ahead and endeavor to anticipate the oil demand for the coming year, and thus determine the volume of oil that can be safely produced without causing major additions to surface stocks. The year has been one of smaller additions to stocks than in 1927, a record demand for oil products, and a further developed spirit of cooperation among oil producers, as well as various other achievements. It is well to pause and take stock of ourselves. Present Status of Crude Oil Supply and Demand The total daily new supply of oil is at this time1 about 2,960,000 bbl. per day, made up of 2,585,000 bbl. domestic crude production, 125,000 bbl. casinghead gasoline, and 250,000 bbl. of imports. With the present low consumption, due to the falling off in the winter season demand, it is estimated that about 150,000 bbl. a day are now being run to storage, and that the first three months in 1929 will see large-sized additions to storage. Consumption plus exports of oil have increased at a regular rate from year to year, and although oil production in 1928 passed the 1,000,000,-000 bbl. mark for the second time in the history of the United States, with a production of 25,000,000 bbl. more than in 1927, only 30,000,000 bbl. were added to storage during 1928. This is compared to an addition of 65,500,000 bbl. in 1927.

Jan 1, 1929

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.' It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12'13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH'S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.' The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By AIME AIME

FRIEND recently remarked that the career of Scott Turner is characterized by Work and Wild -A Ducks. To these might be added Accomplishment and Persistent Fishing. All of these elements are manifestations of his character. The diversions-hunting and fishing-are in the nature of the proverbial trolley conductor's holiday, for many of Turner's years have been spent in the outdoors, often in distant lands, as in Spitzbergen, where the ducks pictured below were bagged. The election of Scott Turner to the presidency of the Institute marks the culmination of a quarter century of membership, during the last two years of which he has been vice-president. He was born at Lansing, Mich., on July 31, 1880, and received his A.B. at the University of Michigan in 1902, with a B.S. and E.M. at the Michigan College of Mines in 1904. Since then he has been granted two honorary degrees, D.Sc. from the Colorado School of Mines, and D.Eng. from the University of Michigan, but he still prefers to be called "Scott" rather than "Doctor." Government service was not a new experience for Turner when he was appointed Director of the U. S. Bureau of Mines by Secretary Hoover in 1925, for his first employment after graduation was as Field Assistant in the U. S. Geological Survey in Oregon and Idaho. This was followed by work in Tombstone, Ariz.; then his first foreign engagement in 1905-6 as superintendent of the San Pablo Gold Mining Co. in Panama. Various field experiences followed, though there was an interlude in work of a kind that few mining engineers ever experience. This was in technical journalism, for in 1906 he was

Jan 1, 1932

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.' Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,' potentiometric3 and scaled flow models' were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy's law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon&apos;s process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By M. E. Wadsworth, W. H. Dresher, W. M. Fassell

HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.&apos; The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.&apos; National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 sphalerite,4 galena," and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,6 ho found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo++ in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit&apos;s construction and operation have been discussed elsewhere,&apos; only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By H. Q. Golder

With the development of open-pit mines of ever increasing depth, the stability of the pit slopes in soil and rock is of growing economic importance. How is it, considering the newness of the problem that we know anything at all about the stability of man-made slopes? How much do we know and how did it all begin? We can make a reasonable estimate of the stability of a slope in soil, but we know as yet woefully little about slopes in rock because the problem is much more complex. It is only with the development of the capacity of the computer to handle wearisome calculations that any but the simplest of stability problems in rock have become possible of solution. But what we do know is a guide of immense value in the design of slopes in rock. But remember that the computer is a great elevator; it takes everyone&apos;s feet off the ground! So our study began with soils and what is now known as "Soil Mechanics", which is a translation of the German term "Bodenmechanik". It is a pity that the title of Terzaghi&apos;s book "Erdbaumechanik" was not used instead. But here the task of the translator is difficult because English lacks the facility of German to string together several words and make a new one whose meaning is unequivocal. Thus, we have the three German words &apos;Erde&apos; &apos;Bau&apos; and &apos;Mechanik&apos;. &apos;Erde&apos; means "earth" in almost all the English senses including "soil". &apos;Bau&apos; and &apos;bauen&apos; convey the meaning of building and construction, and &apos;Mechanik&apos; means "mechanics" which includes statics and dynamics and the &apos;mechanics of materials&apos;, etc. So that a correct translation of the German is a phrase like "the mechanics of construction with, in or on, earth or soil." However we are stuck with &apos;Soil Mechanics&apos; and that is where it all began. Now this study or subject did not begin with &apos;Terzaghi&apos; although his contribution to the subject is unquestionably greater than that of any other single person. Every scientific discipline has its &apos;classical problem&apos; and that of soil mechanics is &apos;the earth pressure problem&apos; and it began in the 17th century. In fact, it probably began before this with the introduction of gunpowder to Western Europe in about the 15th century, but the first known reference to the problem was by Vauban, a distinguished French military engineer who lived from 1633 to 1707 and who gave rules for the dimensions of retaining walls from 6 to 80 ft. in height. The soil properties were not mentioned by Vauban probably because the rules were intended to be applied to fortifications only, but Poncelet (1840) claimed that Vauban&apos;s rules were based on a theory, and not simply on military and practical

Jan 1, 1972

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By Frederick W. DeVries

Since we first agreed to present this talk we have learned that some of you may have been covering ground we intend to discuss: Bob Schechter, Daryl Tweeton, Don Seidel, Herb Burgman; however, the ideas were original when we began, "novel" as in the title of the talk, and whether our results are news or merely corroborative, we feel they point a direction that could be valuable to all. We worked with many of you in the past on using hydrogen peroxide in in-situ uranium leaching. Our talk today is not directly related to peroxide; it is, I hope, illustrative of Du Pont&apos;s interest in providing service to this industry in any way we can. The scouting work we are presenting was stimulated by field inputs: First, ammonium carbonate leaches cause restoration problems, primarily because ammonium ions exchange on clays with calcium. Second, sodium carbonate solutions, especially in South Texas deposits, can cause intolerable swelling of clays. From discussions with Dr. van Olphen, who wrote the book on clay chemistry, we inferred by comparison of the radii of the hydrated ions of the elements in these clay systems, that since potassium had about the same radius as ammonium, and sodium was much larger, potassium occupied a unique position to solve both problems. We have shown: FIGURE 1 Potassium bicarbonate systems leach uranium without loss of permeability found with sodium Potassium salts are very effective in restoring ammonia-leached sites Before reviewing the details of our work, which was performed by Hazen Research, Inc., I should like to stress its scouting nature. We are trying to assist the in-situ industry by pointing out new, potentially important directions. But, as with our previous work on sodium silicate to restore permeability, we feel the development phases can generally best be carried out in cooperative programs with companies directly involved with operations. DISCUSSION Test Parameters Now for the details: Our leaching tests were designed to note pressure-drop changes across the ore sample as the uranium was leached. Figure 2 shows the apparatus. The [ ] packed length was 20.5 inches (52 cm) with fifteen hundred grams of ore in the two-inch (5 cm)-diameter bed. Pressure drop was measured by manometer and feed rates were maintained constant with a tubing pump. The samples, from a South Texas leach site, were sealed in "Zip Loc" bags, frozen with "dry ice", crushed (still frozen) through six mesh, and blended before placement into the columns. The ores analyzed as shown here: FIGURE 3 Ore Analyses [Sample A Sample B U308 015% 0122% Mo 0004% 0086% Se0012% <0001% Fe3,078%076% Fee- 098% 044%]

Jan 1, 1979

By W. S. Ayres

BACK in the early nineties the old Dickerson iron mine in Morris county, N. J., was operated by a vertical shaft 850 ft. deep and by a continuing slope for more than 1000 ft. more 011 an incline of 65", together making the vertical depth about 1800 ft. I was then the general superintendent there. This mine, named for a former governor of New Jersey, had been worked more or less continuously from long before the American Revolution and up to this particular time. The pumping equipment was of the old-time Cornish type, with its long pump-rods running down the vertical shaft and the slope to the sump at its bottom. It was operated by a large flywheel engine in the engine room and all angles were turned by the usual bobs. Saturday was the day fixed for lowering the "suction" into the deepened sump at the bottom of the advancing slope. The mine foreman had gone down with the morning shift to superintend this very vital and particular work, which consisted not only of lowering the "suction" into the sump immediately after the pump had been stopped, but of securing it to the rock and putting in the added sections of column-pipe and of tightening up the numerous bolts at their joints, all before the water rose to the point of working. At an appointed time during the forenoon I had agreed to go down into the mine and join the mine foreman in consultation over any difficulties that might have arisen. At the time agreed I went down by the cage to the bottom of the vertical 850-ft. shaft, and then by ladders down the slope for over 1000 ft. more.

Jan 1, 1930