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By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.' Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith' examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn's suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.'" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year's figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By A. J. McEvily, R. C. Boettner, C. Laird

The processes leading to fatigue failure in the low-cycle range were studied to obtain an understanding of the basis of Coffin's law. Particular attention was paid to the manner of mack nucleation and to the determination of the portion of the total lifetime spent in crack propagation. It was observed that cracks are nucleated at surface notches meated during reversed plastic deformation, Principally at grain boundaries, and that crack growth occupies greater than 75 pct of the fatigue life. When inclusions are present, they are often the primary sites of crack initiation. From consideration of the incremental distances advanced by a crack in each cycle and of the lifetimes of different materials, it appears that the universality of Coffin's law arises from the similarity of crack-tip strain for a given applied strain amplitude, irrespecti7:e of material. STUDIES of low-cycle fatigue have been particularly rewarding in that a simple correlation between fatigue lifetime and plastic-strain range has been shown to exist. This empirical relationship takes the forml,2 Nner=C [1] where N is the number of cycles to failure, Er is the plastic-strain range defined as the total plastic strain per cycle (the sum of the tensile plastic strain plus the compressive plastic strain), n, the exponent, is a constant independent of the material to a first-order approximation and often has a value of about 0.5, and C is a constant which for a number of ductile and metallurgically stable materials is approximately 0.65 for fully reversed strain.3 This relationship has been shown to be valid for a wide variety of metals and alloys and is often referred to as Coffin's law. However, it is yet not clear why so many different metals and alloys exhibit the same over-all behavior in the low-cycle range. Less is known about the mechanisms of fatigue failure in the low-cycle range than in the high-cycle range, but it is expected that the processes would have much in common. For example, an important characteristic common to both high-and low-cycle ranges is that fatigue crack propagation can occupy a considerable portion of the total lifetime. This has been shown by Laird and smith4 by a count of the number of ripples present on the fracture surface of copper specimens, each ripple corresponding to one cycle of load. On the other hand, some marked differences have been noted. For example, in copper,5 nickel, and aluminum4 there is a greater tendency for grain boundary cracking to occur as the strain amplitude is increased. The purpose of the present work was to study further the processes leading to fatigue failure in the low-cycle range and to obtain an understanding of the basis for the validity of Coffin's law. Particular attention has been paid to the manner of crack initiation and to the determination of the portion of total lifetime spent in crack propagation. MATERIALS A number of metals and alloys were tested, although more attention was focused on a particular few, once general trends had become apparent. Alloys were selected so as to investigate the effects of crystal structure, number of phases, stacking-fault energy, and impurity content. The materials in this grouping were: high-purity copper OFHC copper 1100 aluminum (commercially pure) 70-30 brass (Cu-30 wt pct Zn)

Jan 1, 1965

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By H. A. Koch, R. L. Slobod

This paper discusses a new oil recovery process called the "miscible slug process." This process involves the injection of propane or LPG into the reservoir prior to gas injection. The operating conditions are maintained so that the slug is miscible with both the reservoir oil and the injected gas phase. Thus, a miscible phase displacement is achieved, and high recoveries are obtained from the area of the reservoir contacted. The most striking discovery of the laboratory study which included displacements from cores up to 123 ft in length was that relatively small slugs of LPG are effective over reservoir distances in the miscible displacement of oil. This makes possible the commercial application of the process. The important factors controlling the size of the slug are: (I) reservoir length, (2) reservoir fluid composition, and (3) reservoir pressure at the displacement front. Of lesser importance are the effects of injection rate and porous medium type. Questions which have not been completely answered deal with the effects of gravity and reservoir inhomogeneities on the process. INTRODUCTION One of the major problems facing the oil industry today is recovery of the large fraction of the discovered oil which will remain unrecovered unless some new processes are found. Water flooding has been one successful method used to increase recovery over natural depletion. But even successful water floods may leave 25 to 40 per cent of the pore space filled with residual oil. Recently a process which involves the use of thermal energy has been reported1,'*' which may prove useful in increasing recovery from shallow reservoirs containing highly viscous crudes. This paper deals with a new oil recovery process involving use of miscible phases to displace the oil from the reservoir. Miscible phase displacement oil has been an intriguing idea because the elimination of capillary effects in the reservoir leads to 100 per cent recovery in the areas contacted by the miscible displacing phase. The big deterrent in the past to the practice of miscible phase displacement has been the high cost involved in using large volumes of solvent in the process. The use of high pressure gas to achieve a miscible phase displacement of reservoir oil has been reported4,5 as one economically feasible method. However, this process calls for the maintenance of pressures above 3,000 psi at the dis-placement front. The process described in this paper is not restricted to high reservoir pressures; the only qualification being that the slug of material which is injected into the reservoir must be miscible with both the displaced oil 2nd the displacing phase. Two such cases are the use of an alcohol slug followed by water to achieve a mis-cable water flood, and the use of a low boiling hydrocarbon slug such as propane followed by gas to achieve a miscible gas drive. This paper will deal specifically with the propane dug process. This process will obtain a miscible phase displacement at pressures as low as about 1,200 psi at a reservoir temperature 01 150°F. The process is very simple. The propane displaces oil completely at one front because it is miscible with the oil, and gas displaces the propane completely at a second or trailing front because it is miscible with the propane. A small band of propane should thus remain wedged between the gas and oil phases. This idea has been called the "miscible slug process."6 Unfortunately, the propane slug will become diluted as it flows through the reservoir. This results from a mixing action since the fluids flow through a complex reservoir porous medium rather than simple capillaries. Fig. 1 diagrams a miscible slug displacement. The effects of some of

Jan 1, 1958

By Christopher G. Atwater

The object of this paper is to describe and discuss the progress that has been made, up to the present date, in the development of the modern by-product coke-oven. There are few members of the Institute who have not heard more or less of the by-product oven-installation, and there are many whose acquaintance with it is intimate and practical. Since the general opinion on the subject has hardly become crystallized as yet, it is hoped that this paper will at least furnish matter for discussion. In order to obtain an idea of the present status of the industry in the principal iron-producing countries, the following table has been prepared : Table Showing Proportion of Coke Made in By-Product Ovens in Various Countries. United Kingdom (1898, Mr. George Beilby). Short Tons. Per Cent. Coal coked in by-product ovens,. .. 1,400,000 7.9 Coal coked in blast-furnaces with by-product recovery,.......2,240,000 12.7 Coal coked in non-by-product ovens,. . 14,000,000 79.4

Jan 1, 1903

By C. H. Herty

The reactions that occur in the basic open-hearth process are complicated and are subject to many different factors such as temperature, slag composition and rate of boiling of the bath. It is difficult, therefore, to present an extended theoretical discussion of open-hearth operations without confusing the theory of the process with the application of the theory. This paper attempts to present some of the theory of the open-hearth process without mentioning theory at any point, simply giving some of the practical applications of results founded both on theory and practice and on experimental work both in small and large furnaces. It is hoped that an answer to a number of questions commonly asked by the open-hearth operator may be found in this paper. Discussion of the subject matter is taken up more or less in the order in which a heat ie worked, beginning with the oxidation of the scrap charged, sulfur absorption by the scrap, calcination of the limestone, and extending into the pig iron for the charge, the slags formed during the process, and some of the phenomena occurring in deoxidation of the steel and in its action in the molds. Oxidation of Scbap When scrap is charged into a furnace it immediately begins to oxidize, Oxidation is carried out by.three reactions: Fe + H20 + FeO + Hz (absorbs heat) (1) Fe + C02 + FeO + CO (absorbs heat) (2: Fe+ ½O2 + FeO (gives off heat) (3: The product of oxidation contains some Fe3O4, but FeO usually predominates on account of the iron present in close contact with the scale formed For a given type of scrap the amount of oxidation is controlled by thc fuel and by the excess air being carried in the furnace, the temperature 01 the furnace, and the length of time that the scrap is in contact with the furnace gases. In general, less oxidation occurs when the furnace is rur hot so that the scrap melts rapidly. More important in operation thar the two variables atmosphere and temperature, is the type of scrap being

Jan 1, 1929

By Arne Westgren

ONLY in exceptional cases can the ordinary methods of chemistry be used for determining the constitution of compound metallic substances. Recourse has therefore been taken to special methods, the main expedients of which are, as we know, thermal analysis and metal microscopy. To these may be added-though more accessory-the determination of electric conductivity, specific volume, hardness or other properties. The information obtained by these methods has been compiled in equilibrium diagrams. Naturally, the technically most important alloys, such as steel, bronze and some others, have been subjected to very close study, and many investigators have devoted themselves to the solving of their problems of constitution. The equilibrium diagrams of these systems are therefore known today with a comparatively high degree of accuracy, even though it must be admitted that many details regarding their transformation reactions still remain to be completely explained. The equilibrium diagrams of the other alloys as a rule have not been determined so accurately. Most of them are based only on approximate determinations of the homogeneity ranges of the various phases. Thus extensive, detailed studies remain before these diagrams may be considered as established. Unfortunately, it must also be admitted that many of the alloy diagrams given in the present handbooks are as a whole very dubious. As a matter of fact, many of them may really only be viewed as the results of rather superficial, orientating investigations. In fact, there also seems to be a general opinion prevailing in our day that much work still remains to be done before the equilibrium conditions of the alloys may be considered as fully explained. At present, in almost all institutes for research on metals, as well as in many university laboratories, investigations to this effect are being carried out. As a rule, the classical methods of metallography, the thermal analysis and metal microscopy are applied.

Jan 1, 1931

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney's mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling's Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By Ingvar Janelid

13.7-1. General. Iron ore mining in western Europe is mostly carried out underground and only a minor part is mined by open pit methods. Actual open pits of importance in this connection are, among others, Svappavaara in Sweden, Mo i Rana and Sydvaranger in Norway, Corby Mines, Colsterworth, and Scunthorpe in Great Britain, and in western Africa, Nimba and Bong Range in Liberia, and Kedia d’Idjil in Mauritania. The open pit mines of western Africa are of great interest in this connection as they are designed according to European practice and have accepted the same techniques, methods, equipment, etc. as the European mines. In the surface mining of limestone, granite, shale, etc., the technical conditions generally are similar with those in the iron ore mines. Some information will therefore be submitted from typical quarries. The geological conditions at the various iron ore mines and limestone and other quarries vary extensively. In Scandinavia the iron ores occur exclusively in Precambrian rocks. The ore is hard, mostly magnetite or hematite, folded and steep dipping, and hence accessible to surface mining only in the shallow sections. In the mines referred to, open pit mining will last for another 10 to 30 years, whereupon mining has to be continued by underground methods. In France the Minette iron ore has previously been mined in open pits but, because of increased overburden, mining underground with room and pillar methods now dominates. The iron ores are Jurassic, flatlying strata of oolitic type, containing chamosite, siderite, and brown hematite. The British iron ores are mostly of the same origin and appearance as the French deposits, but despite heavy overburden they are preferably mined from the surface. In western Africa, the iron ores are of the same type as in Brazil, i.e., itabirites with high-grade portions resulting from silica-leaching and weathering. The ore contains mostly brown and blue hematite and magnetite. Nimba and Kedia d’Idjil are very similar regarding ore quality and geology. Bong Range is a deposit of low-grade ore which has to be concentrated.

Jan 1, 1968

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

All pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process,9-11 but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open- circuit roughing and closed-circuit roughing are best defined by the diagrams.

Jan 12, 1958

September 1 to 6, 1918 COMMITTEE IN CHARGE Spencer Penrose, Chairman. George M. Taylor, Vice-Chairman. A. E. Carlton, Chairman. Finance Committee J. Dawson Hawkins, Secretary DENVER COLORADO SPRINGS CRIPPLE CREEK Finance Finance Thomas B. Crowe T. B. Stearns A. E. Canton , E. P. Arthur, Jr. Richard A. Parker Spencer Penrose N. S. Greensfelder T. B. Burbridge George M. Taylor A. E. Carlton. A. L. Blomfield, Treasurer B. F. Hill Arrangement I F. G. Willis Dave G. Miller Registration Norris E. Eads Frank Bulkley Loren C. Lennox 1V. E. Ryan Geo. E. Collins Horace F. Lunt Fred Jones .1. M. Tippett F. D. Smale Entertainment J. H. Haynes F. H. Bostwick Arrangement and Entertainment L. W. Lennox F. E. Shepard George M. Taylor A. L. Blomfield M. R.. Valentine Howland Bancroft J. D. Hawkins Thomas B. Crowe B. P. Morse A. E. Carlton E. P. Arthur J. G. Perry G. H. Clevenger Etienne A. Ritter Ladies Ladies , PUEBLO Mrs. T. B. Stearns, Mrs. C. M. Taylor, Mrs. C. H. Clevenger J. F. Welborn Chairman. Chairman H. B. Carpenter Mrs. C. Loughridge Mrs. S.-Penrose Mrs. A. E. Carlton L. B. Eames Mrs. H. Bancroft Mrs. J. D. Hawkins Mrs. A. L. Blomfield F. Robinson Mrs. G. Bancroft Mrs. L. C. Lennox Mrs. J. M. Tippett . Mrs. W. D. Leonard Mrs. H. F. Lunt -Mrs. E. C. van Diest Mrs. C. Chase Mrs. E. A. Ritter Mrs. AV. Strieby Mrs. F. H. Bostwick Mrs. L. S. Harner Mrs. C. L. Bailey Mrs. F. Bulkley Miss F. Dickerman Mrs. E. P. Shove Mrs. C. L. Tutt Mrs. F. C. Peck Mrs. F. D. Pastorius

Jan 10, 1918

(Read at the Amenia Meeting, October, 1877.) THE Committee on a Standard Gauge have been constantly engaged, since their appointment, in the duties assigned to them.§ They have corresponded with different persons interested in the manufacture and use of gauges in this country, and have received from several of them important information. They have also entered into correspondence with the governments of England, France, Germany, and Russia through their Consuls, and with Austria directly. The Consuls of Germany and France * Transactions, Vol. V, p. 575. t Transactions, Vol. III, p. 43. + Transactions, Vol. II, p. 224. §See Transactions, Vol. V, p.,48.

Jan 1, 1878