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By R. E. Gilchrist, R. F. Nielsen

When a gas is displaced by mother in a porous medium, and there is a relative immobile liquid present. there is a transition zone in which the gas composition varies from essentially that of the original gas to that of the injected gas. The change in extent of this zone with time may be governed by a mixing process in the direction of flow and by the rate of establishment of gas-liquid equilibrium, if the gases are appreciably soluble in the liquid. The relative importance of these two factors in deterri~ining the growth of the transition zone is discussed, with appropriate equations and experimental data. INTRODUCTION The various solution methods of oil recovery involve a transfer of the components of a mixture, whether within a single phase or between a liquid and gas. The similarity of a natural porous medium to systems used in separation and chromatographic processes makes it seem reasonable that certain concepts used by chemical engineers in "mass transfer" might be applicable to petroleum reservoirs. One approach, the HETP (height equivalent to a theoretical plate), involves a distance or length of time over which equilibrium might be con. sidered as established. Another approach involves direct use of a rate of mixing or rate of establishment of equilibrium. The latter approach has been preferred in relation to production problems. DISCUSSION AND PROCEDURE When a gas or liquid in a porous medium is displaced by one of different composition but miscible with it there will be set up a transition zone in which the composition varies from cssentially that of the original fluid to essentially that of the injected fluid. If the fluid being displaced is a gas, and there is a relatively immobile liquid present, the transition zone may be

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933

By Waldemar Lindgren

THE following pages present data accepted by many geochemists and geologists regarding the succession of minerals and the temperatures of formation in ore deposits affiliated with igneous rocks. They also present the individual views of the author on the composition of the solutions that were active and on the mode of deposition. He does not regard these views as speculations or hypotheses but as forming a well motivated and consistent theory. It is not certain, however, that all investigators will subscribe to them.

Jan 1, 1936

By Euzebio De Oliveira

ONE of a recent batch of samples from the Serra da Baliza, in the state of Parana, Brazil, contained asphalt and a dark heavy oil; and workmen on the railway from Porto União to Uruguay discovered asphalt, coming from eruptives that outcrop along the Rio de Peixe. The occurrence f asphalt in the triassic eruptives of southern Brazil, however, has been known a long time, according to Dr. Gonzaga de Campos. It is generally believed that the Botacatú sandstone is always a hard vitrified rock, from the metamorphic action f. the overflowing eruptive contacts. In this region, however, the contact metamorphism is almost nil; the sandstone is slightly hardened in a narrow zone about 20 to 30 cm. wide. In many places, the sandstone is so friable as to be easily reduced to sand, which is used-.in, mortar for building in Guara-puava and Palmas. South and west from Porto União,. this bench of sandstone is about. 50 m. thick, and is capped by a heavy bed. f basic eruptives, many of which are amygdaloids. Dr. Geo: P. Merrill, after studying the triassic eruptives collected by the Coal Commission, reached the conclusion that. "All these rocks are of typical basalt-diabases, not in any essential different other than in structure. An interesting mineralogical phase is its paucity in olivine, which in many cases is completely lacking. Professor Hussak, who carefully studied these rocks and their accessory minerals, decided that in the dikes they are granular (diabase) and, that in the lava sheets, porphyritic (augite-porphyrite or melaphyre), and that the latter pass evidently to normal diabases and are always typical of effusive rocks. The examination f many slides from dikes and sheets leads us to adopt the opinion of Professor Hussak; the rocks of the dikes are of ophitic structure, while that of the sheets show a great variety f structure and may vary from almost granular to basaltic. The great paucity in olivine had been noted by Hussak, who classes as melaphyres, the porphyritic triassic rocks in Brazil which contain olivine.

Jan 4, 1921

The Board of Directors, at its meeting on March 22, 1918, extended an invitation to the American .Institute of Metals to become the Institute of Metals Division of-the American Institute of Mining Engineers in accordance with the terms of By-Law VII. This invitation was presented to the membership of the American Institute of Metals for letter ballot, and, at the meeting of the Board of Directors of the American Institute of Mining Engineers on April 26 191 ,it-was reported that the replies had been in favor of accepting the invitation. The American Institute of Metals therefore becomes a division of this Institute and the members thereof are entitled-to all privileges of regular

Jan 6, 1918

The one hundred and twentieth meeting of the Institute was held at Chicago, Sept. 22 to 26, inclusive, and was in every way success although the steel strike against the United States Steel Corpn. prevented many engineers from attending the steel session and made necessary the annulment of the trip to the steel works at Gary on Tuesday. All of the meetings were held at the Congress Hotel, with the excep-tion of the session on Non-ferrous Metallurgy which was held at the Coliseum where the Fifth National Exposition of Chemical Industries was in progress. This session was a joint one with the American Electro-chemical Society. The total attendance, as shown by the registration, was 850.

Jan 11, 1919

By George Straghan, Ralph Thomas

OIL production in Kentucky in 1941 was 5,191,024 bbl., one barrel less than in the preceding year. The total completions for the state numbered 714, of which 256 were gas Manuscript received at the office of the Institute Feb. 26. 1942. * Geologist, .Kentucky Weal Virginia Gas Co., Ashland, Ky. † Geoloneist. Inland Gas Co.. Ashland. Kv. producers, 220 oil wells, and 227 dry holes. The total number was 95 more than in 1940. No new important oil or gas pools were discovered. The number of dry tests was large, although many of the dry holes could be considered wildcat tests. In western Kentucky, 365 wells were drilled, of which 145 were oil producers,

Jan 1, 1942

By Ralph Thomas, George Straghan

OIL production in Kentucky in 1941 was 5,191,024 bbl., one barrel less than in the preceding year. The total completions for the state numbered 714, of which 256 were gas Manuscript received at the office of the Institute Feb. 26. 1942. * Geologist, .Kentucky Weal Virginia Gas Co., Ashland, Ky. † Geoloneist. Inland Gas Co.. Ashland. Kv. producers, 220 oil wells, and 227 dry holes. The total number was 95 more than in 1940. No new important oil or gas pools were discovered. The number of dry tests was large, although many of the dry holes could be considered wildcat tests. In western Kentucky, 365 wells were drilled, of which 145 were oil producers,

Jan 1, 1942

By G. F. Butterworth

The metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to, produce in the stock a physical condition having the requisite properties. The fist group consists of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat treated by giving it a quench and a draw. These barrels will be referred to as " heat-treated " barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent, of manganese, show a single very pronounced point between 1300" and 1350" F. (704" and 732" C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure shown in Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under a low magnification appears almost homogeneous, as in the case of fine grains of pepper and salt well mixed together, Fig. 6. This structure is substantially the same for all

Jan 1, 1920

By W. H. Boyer, J. W. Gabelman

The concept of metal zoning has long been recognized (Spurr, 1907, 1923; Emmons, 1924, 1926; Lindgren, 1933; Rateman, 1950), although it has been considered indistinct for most epithermal districts. The geometric relation of barren zones of hydrother-mally altered rock to ore deposits was emphasized in the work of Lovering (1941, 1949, 1950), Sales and Meyer (1948, 1949, 19501, Burbank (1941, 1950), Schwartz (1939, 1950), and Kerr (1947). Lovering (op. cit.) and Sales and Meyer (op. cit.) emphasized the consistent presence of barren alteration envelopes enclosing individual ore bodies, particularly of the vein type. Schwartz (1950) noted a difference between the distribution of alteration zones described by Lovering and by Sales and Meyer, as compared with those associated with the porphyry copper deposits of the Southwest. The disseminated deposits of the Southwest usually occur within large bodies of altered rock whereas most veins do not. In the following discussion the mineralization process is conceived of consisting of two distinct phases: pre-ore nonmetallic alteration and metallization. In the present investigation the position, size, and shape of all known hydro thermally altered areas and the position, size, and metal type of all known ore deposits were plotted on base maps of southwestern and west-central Colorado (Figure 1). The maps indicate a generally consistent geometric relation between altered and metallized areas. The addition of alteration to the pattern of metal deposits establishes a temperature zoning pattern of much greater clarity than that formed by the epithermal metal deposits alone, and allows a more precise definition of mineral belts. The center of strongest mineralization is indicated to be the area of greatest barren alteration, and metal deposits are grouped about it both under structural control and crudely in response to temperature zoning. The combination of an area of strong alteration and associated marginal clusters of metal deposits is defined as a mineral district. The strong similarity in individual deposits, in groups of different types of deposits, and in the alteration-metallization relation in districts throughout the region implies that a single metallogenic province is represented in southwestern and west-central Colorado. The occurrence of deposits in Tertiary voi-canics indicates a late Tertiary metallogenic epoci., although an early Tertiary epoch is known locally as at Ouray. Patterns formed by mineral districts can be

Jan 1, 1961

By L. Moyd, P. Moyd

The first commercially available portable gamma ray-neutron beryllium detector, the Rerylometer, was developed by the same group that developed the first practical portable scintillation counter, the Scintillo-meter. This group includes Professor George Brownell, of the Geology Department of the University of Manitoba in winnipeg, and his associates, K. I. Roulston, R. w. Pringle, and R. L. Funt, of the Physics and Engineering Departments of the University of Manitoba. A prototype model was tested in the field by Dr. Brownell during the summer of 1958. Commercial production was undertaken shortly thereafter by Nuclear Enterprises Ltd., of Winnipeg, and a license for manufacture and distribution in the U.S. was granted to Isotopes Specialties Co., of Burbank, California, a division of Nuclear Corporation of America. Early in 1959, we were retained by the 'Mining Division of Minerva Oil Co. to Legin a search throughout North America for minable deposits of beryllium, and to train members of their permanent staff to continue the program. The project included literature sur-veys, interviews with members of various federal, state, and provincial agencies, scanning of our own collection of suites of specimens from various mineral occurrences, and the examination of deposits in the field. The value of a beryllium detector to this program was obvious and arrangements were made to procure one as soon as possible, which resulted in our obtaining and using the first instrument that was produced commercially in the U. S. In addition to the commercially available Berylometer, Mr. William Vaughan and his associates, of the U. S. Geological Survey Geophysics Division, in Denver, have developed and tested several experimental instruments based on the same principles. DETECTOR Principles The detection of beryllium is based on the fact that "hard" gamma rays (1.6 MEV and geater), such as those produced by Antimony convert ordinary beryllium (Be9) to Be8 , with the release of a neutron. The neutrons are counted by a scintillator designed to favor neutron responses while suppressing those of gamma rays. 'The instrument is completely selective for beryllium. No other element can interfere. Instrunlentation The Rerylometer itself, which is cylindrical, is about 8 inches in diameter, 13 inches high, and weighs about 11 pounds. (Figs. 1, 2). The principal components include: 1. A disc of wax to moderate (or "thermalize") neutrons. 2. A boron-enriched polyester-zinc-sulphide fluorescent screen. This material produces strong flashes when struck by thermalized neutrons but only weak flashes from gamma rays. 3. A photomultiplier tube. 4. An electronic circuit, complete with one srnall 71/2-volt dry battery. The photomultiplier tube and electronic circuit convert neutron flashes to electrical impulses, but gamma ray effects are almost

Jan 1, 1961

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

US 4,132,635 -In the froth flotation beneficiation of low- grade siliceous iron oxide ore, an aqueous pulp of undeslimed ore is conditioned first with a reagent formed by incorporating a water-soluble polyvalent metal salt into an aqueous solution of sodium silicate and then with oleic acid or other anionic collector and optionally pine 011 or other frother. The conditioned pulp is subjected to flotation to concentrate Iron oxide values in the froth D. C. Yang, assigned to Michigan Technological University Jan 2, 1979 7 pp (209-1 66) Filed 1-1 3-77 (759,094) Drawing below.) [ ] US 4,133,038-In the froth flotation beneficiation of copper sulfide ore or other ores, an aqueous suspension of a mineral sample of uniform grain size and composition is conditioned with a strongly adsorbable collector in an amount which is a fraction of the amount sufficient to create a monomolecular layer on the mineral grains, and the conditioning continued until the entire amount of collector is adsorbed The conditioned pulp is subjected to flotation, the floated particles separated at timed intervals, and the flotation rate coefficient determined. By varying the degree of adsorption in repeated treatments, the dependence of the flotation rate coefficient on the degree of adsorption may be determined A Nieml Jan 2, 1979 10 pp (364-502) Filed 12-7-77 (858,353) Priority Finland, 5-26-75 (75/1,525) Same: British 1,533,723, dated Nov 29, 1978 Same Canadian 1,065,066, dated Oct 23, 1979 US 4,133,746System and method for maintaining substantially steady state conditions in the froth flotation beneficiation of copper ore, molybdenum ore, or other metal ores The mass flow of flotation concentrate from the cell is monitored continuously, and the rate of admission of aeration air into the pulp in the cell is varied inversely with respect to variations in the mass flow control of rougher flotation cells is accomplished with a single valve G W Dopson, assigned to Magma Copper Co Jan 9, 1979 6 pp (209-1) Filed 11- 23-76 (744,306

Jan 1, 1980

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By J. F. Wilson

An experimental investigation has been made of gas-driven slug displacements in a system of high gas saturation to evaluate the process for use in a California reservoir. Fluid compositions, temperature, pressure and core permeability duplicated reservoir conditions as closely as possible. The temperature was above the critical of the slug materials. The slug composition required for 100 per cent oil recovery in the linear flow systems was found to agree with that determined from equilibrium phase studies. A qualitative theory for the slug displacement of two-phase systems is proposed and found to be in general agreement with the observed flow behavior. The theory predicts that the length of the reservoir fluid-slug transition Zone will increase with increased initial gas saturation and decrease with increased oil swelling accompanying the composition change from reservoir oil to the critical composition. The precipitation of small amounts of an asphaltic phase during the formation of the transition zone had no adverse effects on the flow behavior of otherwise miscible systems. INTRODUCTION Despite the large number of recent publications relating to oil recovery by miscible displacement, little information is available concerning the behavior of crude oil-natural gas systems at conditions likely to be encountered in field application. The laboratory data reported here were obtained during an investigation of the possibility of using a gas-driven LPG slug in a partially depleted California reservoir. Seven gas-driven slug displacements employing slugs of different compositions and sizes were made in 26- to 27-ft long sandstone cores. The equilibrium phase behavior of the systems was also determined. The features of primary interest in this study are the following. 1. Data were obtained on the displacement of reservoir fluids at reservoir conditions. 2. A high gas saturation existed in the long cores at the start of the displacements. 3. The temperature of the studies was above the critical of the slug materials. 4. A comparison between the flow behavior and equilibrium phase behavior, as illustrated by a pseudo-ternary phase diagram, is afforded for a system of considerable complexity. THEORY Phase Behavior The use of the pseudo-ternary phase diagram to illustrate the phase behavior in miscible displacements has been discussed by Clark, Schultz and Shearin. Sie-vert, Dew and Conley and Arnold, Stone and Luffel' have presented both phase equilibrium and flow data for true ternary systems. For the true ternary, the application of the theory is straight-forward; for a reservoir system represented as a ternary, the theory undoubtedly gives a qualitatively correct picture. One purpose of this investigation was to see if the pseudo-ternary phase diagram could be used to predict with reasonable accuracy the conditions necessary for miscible displacements with actual reservoir systems. MiscIBLE Displacement of Two-Phase System A large number of papers "I3 have treated the miscible displacement of a single-phase fluid from both an experimental and a theoretical viewpoint. However, the normal field application of the process will be in a partially depleted reservoir. Often the state of the system will be such that the mobility of the gas phase is greater

By J. F. Havard

The enterprises based upon the industrial minerals are diversified in geologic habit, mining systems, processing techniques and marketing methods. Nevertheless, in 1972 these enterprises faced many of the same frustrations and hopes and knotty problems and crucial decisions. Volume and profits were generally improved but were uneven in extent and effect. The U.S. cement industry, for example, was unable to meet demand in major markets. It was constricted by a frozen low-level price structure, faced expensive pollution control measures and watched heavy imports penetrating its markets from several European nations, Mexico and Canada.

Jan 1, 1973

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy's obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:'l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By W. C. Phalen

The production of salt in the United States divides itself at the outset into two distinct classes…

Jan 1, 1915