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By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By M. W. Burkart, B. Lustman

Uranium-base alloys exposed to high temperature water fail either by uniform oxidation or by sudden cracking and disintegration of the metal. The disintegration results from the oxidation of a second phase which is precipitated during the corrosion process. The precipitate has been identified as a metastable hydride of uranium. URANIUM-BASE alloys consisting of the body-centered-cubic ? phase are susceptible to two different modes of corrosion failure when exposed to high temperature water. In the first process, a smooth oxide film is formed on the metal surface which continually flakes off during exposure and results in a uniform weight loss of the specimen. The oxide is present as a thin, adherent layer whose thickness remains approximately constant. As the metal oxidizes during corrosion, a nonadherent layer is built up on this film and continually sloughs off. Coincident with the uniform corrosion just mentioned, another process occurs which eventually leads to failure of the metal by cracking and general disintegration. The failure takes place during a relatively short time compared to the total exposure. To distinguish this type of failure from the uniform corrosion, the cracking or disintegration of the metal will be referred to as discontinuous failure. For the ? phase uranium alloys it is discontinuous failure rather than uniform corrosion that limits the useful corrosion life of the alloy. This paper will be concerned primarily with the mechanism of discontinuous failure. Physical Changes During Corrosion—The alloys used in this investigation were ? phase uranium alloys containing 7 to 12 wt pet Mo or Cb. The preparation of the alloys, the method of corrosion testing, and the actual corrosion results are presented in another paper.' The ? quenching treatment consists of annealing the alloy for 24 hr at 900°C in a sealed Vycor glass tube filled with helium and then water quenching to room temperature without breaking the tube. The corrosion behavior typical of a ? phase uranium alloy is shown in Fig. 1. This specimen was a U-12 wt pet Mo alloy tested in pressurized, degassed water at 650°F. The corrosion rate was practically constant at 0.28 mg per sq cm per hr or increased slightly until about 15 to 20 days of exposure, when the onset of discontinuous failure occurred in this particular sample, and the specimen soon began to crack and disintegrate. The simultaneous increase in the observed corrosion rate is a result of the increased area of exposure due to cracking of the specimen. The microstructure of a specimen that failed by cracking is shown in Fig. 2. The presence of a plate-like precipitate can readily be seen. Metallographic examination of corrosion specimens reveals that the onset of discontinuous failure is always preceded by the formation of a plate-like second phase in the ? uranium matrix. Hydrogen analyses of specimens periodically withdrawn from corrosion test reveal that the hydrogen content of the alloy increases on exposure to the high temperature water, as shown in Fig. 3. The hydrogen is available as a corrosion product resulting from the formation of UO2 by the reaction of the alloy with water. Specimens analyzed just prior to discontinuous failure contained as much as 1200 ppm H, whereas the plate-like phase appears to precipitate out at a hydrogen concentration of between 10 and 25 ppm. The observed increase in hydrogen content prior to and during the formation of the plate-like precipitate suggests that this constituent may be a hydride of uranium. Additional evidence linking the identity of this phase to a hydride is that it can be removed by vacuum annealing at temperatures of 100°C and above. Decomposition products of the ? phase would certainly not dissolve at such temperatures, nor could other likely products of corrosion, such as oxides, be dissipated at any of the test temperatures. The precipitation and growth of the second phase during corrosion is accompanied by an increase in hardness of the specimen. The hardness increase results from the dispersion of the harder precipitated

Jan 1, 1959

By Victor Rakowsky

A CLEAR understanding of the factors that deter-mine the consumption of zinc metal is essential to a proper survey of the future of the industry and the relation of the several producing districts. With a view of explaining a sound basis for the consider-ation of some of the problems facing the zinc-mining industry of the Oklahoma-Kansas and Missouri district some of these factors are here set out. The zinc industry of the United States furnishes metal for three major uses, viz.: (1) zinking iron and steel (galvanizing); (2) brass making; (3) sheet rolling. Other important uses are for lead desilverization, the manufacture of castings, including die castings, and the manufacture of zinc oxide by the French process, which consists in burning spelter. The use of zinc for galvanizing comprises the coating of sheets, tubes, wire and shaped products, the latter ranging from chains to buckets. The brass-making industry may be sub-divided into manufacture of red brass, yellow brass and white brass, the percentage of zinc in these products being roughly 30, 40 and 80 respectively. The use of white brass is relatively a new thing and it may attain considerable proportions as a substitute for yellow brass. Ingalls estimated the percentage of total metal consumed for the above purposes in pre-war times as follows: HIGH PRODUCTION RECORD, SHORT TONS USES PERCENTAGE OF METAL Galvanizing 60-65 210,000 in 1912 Brass making 17-20 175,000 in 1916 Rolled sheets 10-12 57,000 in 1917 Other uses 5- 7

Jan 3, 1923

Technical graduate wanted for metallurgical. work in experimental laboratory of large New England manufacturing concern. A knowledge of metallography of steel is essential. Practical experience is desirable but not required. No. 305. Man familiar with precipitating with the diamond drill core to act as foreman. No. 311. Competent mining man to develop and take charge of mines in Peru. Property to be developed from start and equipped with thoroughly modern appliances to meet the increased production. Applicant must possess considerable mechanical ability and experience. No. 312. Engineers and assistant engineers in forest production for National Defense work for the duration of war. Laboratory work conducted primarily by experimental and research methods, embracing principally investigations of mechanical and physical properties of wood, processes for the preservation of wood against decay and other destructive agents, practical problems of pulp and paper industry, and other industries utilizing wood by chemical means or otherwise. Assistance in this department of Government is urgently required in order to obtain maximum benefits from the investigation. Salary $1860 to $3000 for engineers; $1200 to $1800 for assistant engineers. No. 313.

Jan 6, 1918

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By H. C. Chao, L. H. Van Vlack

Small MnS inclusions with known crystallographic orientations were placed inside powder compacts of low-carbon steel. After the metal was axially campressed with negligible end friction, the deformstions for the metal and the inclusions were compared. The MnS inclusions deformed more when the [100] direction was aligned with the compression axis than when the [111] direction was parallel to this axis. The deformations of the inclusions in the two principal radial directions were equal for each of the above orientations. Inclusions with [110] compression alignments did not deform with radial symmetry. The relative deformation of the inclusion and metal was closely dependent upon the relatiue hardness of the two phases. The relative deformation of the two phases was not sensitive to the rate of deformation. RECENT studies by the authors1.&apos; suggested that the plastic deformation of MnS in steel would probably be highly sensitive to the orientation of the inclusions and to the temperature of the metal. This paper reports an investigation of these factors upon MnS behavior within steel. Manganese sulfide (MnS) possesses an NaCl-type structure and typically has extensive (l10) {110} slip as a separate (noninclusion) crystal.&apos; A secondary slip system, ( l 10) { l l l}, has also been observed where the major slip system is restricted. In general, MnS inclusions must be rated as a highly deformable second phase.3 The amount of sulfide deformation varies, however, with several composition and processing factors. Some of these have been only partially assigned. For example, it is known that minor amounts (<0.01 pct) of silicon within free-machining steels will increase the amount of MnS deformation,4 but the mechanism of the added deformation can only be surmised at the present. Manganese sulfide and steel have sufficiently comparable deformation characteristics so that slip which is started in steel may be continued through the sulfide inclusions and back into the steel if the crystal orientations are favorable.5 A more detailed discussion of previous work on the plastic deformation of NaC1-type crystals and on the plastic deformation of inclusions within a metal is given in Chao&apos;s work.6 EXPERIMENTAL PROCEDURE The manganese sulfide which was used in this study was prepared by previously described methods.&apos; Single crystals of MnS, both as cleavage cubes and as spheres, were oriented within steel powder compacts so that the desired crystal directions were parallel to the direction of axial compression. A four-stage hydrostatic compaction procedure was used and involved the following steps. In the first stage part of the powder was placed in a metal die 1 in. in diameter with a thick (1 in. OD, 5/8 in. ID) rubber liner which had one end plugged. The steel powder was hand-rammed, making it as dense as possible before placing a carefully sized MnS crystal (either as a sphere or as a cube) near the center. The crystal was oriented with the chosen direction vertical; viz., [001], [011], or [111], with the aid of a X10 microscope. A pair of tungsten wire threads 0.020 in. in diameter was inserted along the side of this (&apos;core compact" to locate the desired plane after the compression tests. After the crystal was positioned in the center of the die, more powder was added and carefully rammed by hand. The die was then capped with a rubber plug of the same hardness and thickness as that of the liner. The whole assembly as shown in Fig. 1 was compacted by a ram load of 54,000 lb (about 70,000 psi). In the second stage a smaller, 3/4-in, rubber-lined die was used to give a stress of approximately 120,000 psi. The above process was repeated with the initial compact serving as a core for a larger compact. The final product after sintering was a cylinder 1 cm long and 1 cm in diameter, having a density of 7.54 g per cu cm. This was close to the theoretical density since the metal contained a non-metallic phase. There was no evidence of MnS deformation during the hydrostatic compaction or subsequent sintering. Elevated-temperature hardness data were obtained by procedures previously described.2 Compression tests for inclusion deformation utilized the cylinders which were described above. The critical problem in these tests was the lubri-

Jan 1, 1965

[Trans. No. Place Date Vol. Page 1, Wilkes-Barre, Pa.* .... May, &apos;71.. 1 3 2. Bethlehem, Pa Aug., &apos;71.. 1 10 3 Troy, N. Y Nov.,&apos;71.. 1 13 4. Philadelphia, Pa Feb., &apos;72.. 1 17 6. New York, N. Y •.... May, &apos;72.. 1 20 6. Pittsburgh, Pa..:.Oct., &apos;72.. 1 25 7. Boston, Mass Feb., &apos;73.. 1 28 8 Philadelphia, Pa.&apos; May, &apos;73.. 2 3 9. Easton, a Oct., &apos;73.. 2 7 10. New York, N. Y Feb., &apos;74.. 2 11 11. St. Louis, Mo.* May, &apos;74.. 3 3 12. Hazleton. Pa Oct.. &apos;74.. 38 13. New Haven, Conn Feb., &apos;75.. 3 15 14. Dover, N. J.&apos; May, &apos;75.. 4 3 16. Cleveland, 0 Oct., &apos;75.. 4 9] [ ]

Jan 1, 1925

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa May, &apos;71.. 1 3 2. Bethlehem, I&apos;s Aug., &apos;71.. 110 3. Troy, N. Y Nov., &apos;71.. 113 4. Philadelphia, PaFeb., &apos;72.. 117 5. New York, N. YMay, &apos;72120 6. Pittsburgh, Pa Oct., &apos;72.. 125 7. Boston, MassFeb., &apos;73.. 128 8. Philadelphia, Pa.*May, &apos;73.. 23 9. Easton, PaOct., &apos;73.. 27 10. New York, N. Y Feb., &apos;74211] [ ]

Jan 1, 1925

[Trans. No,PlaceDate Vol. Page1 1. Wilkes-Barre, Pa*May, &apos;71 13 2, Bethlehem, Pa Aug., &apos;71110 3, Troy, N. Y Nov., &apos;71.. 113 4. Philadelphia, PaFeb,, &apos;72.. 117 5, New York, N, Y.*May, &apos;72,, 120 6. Pittsburgh, Pa Oct,, &apos;72,, 125 7. Boston, Mass Feb,, &apos;73.. 128 8. Philadelphia, Pa,*May, &apos;73., 23 9. Easton, PaOct., &apos;73., 27 10. New York, N, Y Feb., &apos;74,, 211 11. St. Louis, Mo,*May, &apos;74.. 33 12, Hazleton, PaOct., &apos;74., 38 13, New Haven, ConnFeb., &apos;75., 315 14. Dover, N. J,*May, &apos;75.. 43 15, Cleveland, 0Oct,, &apos;75,, 49]

Jan 1, 1928

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa.*.. *May: &apos;71.. 1 3 2. Bethlehem, Pa Aug. &apos;71.. 1 10 3. Troy, N. I X Nov. &apos;71.. 1 13 4. Philadelphia, Pa Feb. &apos;72.. 1 17 5. New York, N. Y.*.... May, &apos;72.. 1 20 6. Pittsburgh, Pa Oct., &apos;72.. 1 . 25 7. Boston, Mass Feb., &apos;73 1 28 8. Philadelphia, Pa.*.... May, &apos;73 2 3 9. Easton, Pa Oct., &apos;73 2 7 10. New York, N. Y Feb., &apos;74.. 2 11] [ ]

Jan 1, 1925

By Petter Östberg

Having brought with me to this meeting a couple of "Mitis&apos;&apos; wrought-iron castings, I have found that they attracted a great deal of attention from steel manufacturers, and especially from those experienced in making castings, among whom some have said that they felt inclined to "unhesitatingly dcclare their manufacture an impossibility," if they had not seen the samples. The consequent demand for explanation of the method of manufacture has been SO great that I accept with pleasure the request by the President to address the meeting on the subject. My object in this address shall be only to explain the main features of the manufacture, referring those who take more interest in the matter to Mr. Th. Nordenfelt&apos;s paper, read before the British Iron and Steel Institute, reprinted in many American papers, and containing both a historical sketch of the inventions and many interesting details. As the manufacture of castings from steel by others is, at least to some extent, a success, I shall, in my explanations hereafter, refer to wronght-iron, although our mode of manufacture is equally applicable, with corresponding advantage, to steel of any temper. The successful manufacture of castings depends upon several very important matters, besides the necessary skill of the workman. You must have a suitable metal as raw material; you must have an eacient and suitable furnace for smelting, so as not to injure the metal; you must be able to handle the metal in a suitable way, from the time it is ready in the furnace until it is poured into the moulds; you must have a suitable moulding material. I claim that in every one of these different branches we have made great

Jan 1, 1886

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers&apos; vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By F. E. Minshall

FoR more than 30 years California has been one of the three leading oil-producing states. Present daily production of crude oil under curtailment, approximately 580,000 bbl., comes from three general areas: Los Angeles Basin, San Joaquin Valley, and the coastal region of Ventura and Santa Barbara Counties. This state produces approximately two-thirds of its oil from eight large fields, and obtains a daily average production of 48 bbl. of oil per producing well, whereas the average for the United States is but 8.15 barrels. During the closing stages of the first half of 1936, discovery of the Section Ten oil field was made, and credit goes solely to geophysical work. It is the first direct important discovery of oil in California that may be credited to geophysics. This discovery may furnish the cue to the means of discovering several fields in California, particularly in the San Joaquin Valley. It is a question, however, whether returns from geophysical work will play as important a part in the future supply of oil in California as have our former types of prospecting. Explobation Methods of prospecting have progressed in the oil industry through invention or improvement in scientific means of locating and defining structure and because of market improvements in drilling equipment. Present methods of prospecting include: 1. A detailed study of geology in an attempt to locate structural and stratigraphic conditions that would be favorable to the accumulation of oil. 2. Geophysical methods involving the use of the seismograph, torsion balance, magnetometer and electrical methods. (There is still much to be learned in California in the application of geophysical methods.) 3. Use of micropaleontology as an aid in correlation,. The principal improvements in drilling equipment are: 1. The Schlumberger dipmeter, which determines the direction of formation dip in an uncased hole.

Jan 1, 1937

By L. K. Nemeth, H. T. Kennedy

The investigation presented in this paper was performd to develop a relationship between the dewpoint pressure of a hydrocarbon reservoir fluid and its composition, temperature and characteristics of the heptanes-plus fraction. This is part of an over-all program to develop correlations for the essential properties of reservoir fluids with the composition, temperature and pressure. In all, 579 dewpoint pressures, determined experimentally on 480 different condensate systems along with their compositions and temperatures, were obtained from the literature and from previously unpublished sources. Compositions were expressed in terms of mol fractions of methane through heptanes-plus, nitrogen, carbon dioxide and hydrogen sulfide, and the molecular weight and specific gravity of the heptanes-plus fraction. Distribution of the samples assured a good representation of most of the major oil-producing areas in the world. A multiple regression analysis program written for the IBhl 7094 digital computer was used to compare numerous equations and to calculate their coefficients. The final equation containing 11 coefficients resulted in an average absolute deviation of 7.4 percent for all the samples. Segregation of data on the basis of one or more variables did not materially improve the results. The correlation developed is useful in predicting the dewpoint pressure of condensate reservoir fluids from variables normally measured in the laboratory. INTRODUCTION In any discussion of the dewpoint of hydrocarbon mixtures, it should be noted that there are two kinds of dewpoints which must be distinguished. The first type, or normal dewpoint, usually occurs at low pressures as dry gas is compressed to the point where liquid first forms. The second type, sometimes called the retrograde dewpoint, occurs when a gas mixture containing heavy hydrocarbons in solution is depressured until a liquid is formed. The first type, as applied to condensate mixtures, would normally be below atmospheric pressure and would be of no interest in reservoir performance. The second type is of great significance in interpreting reservoir behavior and is the property referred to throughout this paper. Laboratory measurement of dewpoints is laborious, expensive and subject to many errors, and it is desirable to find a reasonably accurate method to predict dewpoint pressures from the composition and other readily available properties normally measured on the fluids. A possible method of calculating dewpoint pressures would be to employ a set of equilibrium ratios (K-values). 1 However, the K-values themselves depend on composition as well as temperature and pressure; presently their use adds nothing to the accuracy of predicting dewpoints. If future correlations provide a significantly better method of estimating K-values for heavy hydrocarbons, they may be of greater use. REVIEW OF LITERATURE In 1944, Olds, Sage and Lacey 2 studied the behavior of fluids from the Paloma field. Properties of seven mixtures were studied at temperatures ranging from 100 to 250 F and at pressures up to 5,000 psia. From the information obtained, the influence of composition and temperature upon the dewpoint was determined. It was found that removal of the intermediate molecular weight components from the mixture resulted in considerable increases in the dewpoint pressures. Results indicated that the effect of changes in temperature was relatively minor when compared with the effect of modifying the mixture by removing the intermediate components. Thus, removal of propane and butanes resulted in an increase in dewpoint pressure more than 10 times greater than a change in temperature from 100 to 250 F. The authors stated that althouah

By R. O. Neal

There are two main sources of the water that floods productive oil or gas sands. The water may rise from the lower depths of the producing stratum, or it may come from beds above or below the oil-bearing formation. Usually the recovery of oil is decreased by water entering the oil sands, and most oil-field waters, especially those of deep wells, tend to foster the formation of an emulsion, which is expensive to treat. This paper deals with a method of distinguishing between waters that encroach upon oil-bearing beds from sources in the same stratum and waters that reach the oil sands from horizons above. In order to remedy effectually water difficulties in oil and gas wells, it is absolutely necessary to determine the source of the invading water. Sometimes evidence such as the structural relations between the strata penetrated by deighboring wells and those found in the well under investigation is not adequate; also, data from drill logs and well records, from mechanical tests made on the wells by plugs, testers, drilling tools, etc., and from tests by chemical indicators such as eosin and Venetian red, may be unsatisfactory, for such data may fail to locate the source of the infiltrating waters. As a resort in such cases, the application of chemical analyses, that is, the comparison of an analysis of the water in question with that of typical waters from the various water horizons in that particular district, has in certain instances proved of value. This method has been used to advantage in the Westside Coalinga field of California, where the source of water may be fairly definitely determined , from its composition. The chief conclusions concerning the chemistry of the oil-field waters in California by G. S. Rogers1 are: "Oil-field water is not necessarily salty, as is generally believed, and may not be even slightly salty to the taste. The degree of concentration of chloride in such water is governed primarily by local conditions and is not affected by the position of the water in relation to oil. Sulfate diminishes in amount as the

Jan 1, 1920

By B. G. Hurd

A liquid-Freon permeameter suitable for making routine permeability determinations on small plug samples is described. The instrument is characterized by simplicity of design and ease of operation, and can be assembled inexpensively from stock items of laboratory equipment. It combines the unique advantages of both liquid and gas permeam-eters while eliminating many undesirable features of both general classes of instruments. Precision and accuracy of the specific Freon permeability measurements compare favorably with results of conventional liquid and gas permeameters. INTRODUCTION The liquid-Freon permeameter described in this paper was designed and built for special investigations of the properties of petroleum reservoir rocks. However, its unique advantages over conventional gas and liquid permeameters make it eminently suitable for routine use in the core analysis of small plug samples. In general, gas permeameters are very popular because of their simplicity of design and ease of operation. However, apparent gas permeabilities are normally higher than true specific permeabilities unless special corrections for gas-slippage are applied. Since these corrections require two or more measurements at different internal gas pressures, much of the time advantage of the specific gas permeability measurements is lost. Liquid permeability measurements, on the other hand, require no slip correction, but liquid saturation of the sample is time-consuming and difficult to insure. Often, too, the saturating liquid must be extracted or dried from the plug before it can be used for another experiment. The liquid-Freon permeameter described herein retains the inherent accuracy of the liquid permeameter, while affording the speed and ease of operation of the gas permeameter. Freon-12 (dichlorodifluoromethane) is a haloge-nated hydrocarbon, immiscible in the liquid phase with water. It may be considered as an oil phase in laboratory fluid-flow studies. Like butane and propane, it is a gas at normal room temperatures and atmospheric pressure but can be liquefied at moderate pressures. Complete liquid saturation of a plug sample with any of these fluids can be easily achieved by condensing vapors in the sample and operating the permeameter at a pressure above the vapor pressure of the liquid. Freon-12 is superior to butane or propane for permeability measurements only in that it is relatively nontoxic and completely incombustible, and thus presents no fire or explosion hazard. Freon-12 is believed to be completely nonreactive with most petroleum-reservoir rock samples. It volatilizes immediately from a plug on depressurizing to leave a clean, dry sample suitable for subsequent experiments. Thus, the inherent risk of changing physical properties of rock samples by cleaning and drying operations between permeability measurement and subsequent experiments is eliminated. DESCRIPTION OF THE PERMEAMETER The design of the liquid Freon-permeameter is shown schematically in Fig. 1. Regulated nitrogen pressure caps are used both as a driving pressure

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By Hugh Henton

THIS paper is the result of an investigation made in association with Dr. Charles H. Fulton. Early in 1918 a search was started for methods of utilizing, in the manufacture of basic refractories, certain domestic resources in magnesites, dolomites, and magnesian limestones. Much information was collected during that year and during 1919 regarding magnesite and dolomite deposits. During 1920 and 1921 a research was made into methods of calcining dolomite and separating magnesia therefrom. Some success was attained and many new ideas were brought out in connection with the preparation and utilization of magnesia in the form of "caustic" or light-burned material as well as in the form of refractory or "dead-burned" material. Stimulated by this success, much advance has been made in manufacturing processes for the "plastic magnesia," so called, used for magnesia cement, stucco, flooring and otherwise in the structural industries.

Jan 3, 1926