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By T. F. Witherbee

In a paper read at the Lake Superior meeting, August, 1580, an account was given of the successful use of Rendrock. and Monaky powder upon a .scaffold- and salamander in the furnace. On April 5th, 1881,' the same trouble called for like treatment, which, though not so immediately successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and Sew Bed magnetite, and Kearney red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January lath, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman $ Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateaugay, and East-shaft ores, up to February 224 and from that date Chateaugay and New Bed, the product falling off 9,8, tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here. It required to properly flux it at least 140 per cent. of limestone; and 101 per ent. was actually used. March 11th, all Chateaugay ore aid 80

Jan 1, 1882

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,' it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.' A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.? Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation ;2,3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

E. K. Landis, Philadelphia, Pa. (communication to the Secretary) : Mr. Firmstone's paper is of great interest; but he has unfortunately otnitted to state the most important point, viz., the percentage of sulphur in the two materials he compares; and this omission vitiates the conclusions which he draws. Comparing by grade, instead of silicon-contents (as in his Table III.), the iron made using limestone with that made using dolomite, we find for gray-forge the average of four analyses under limestone to be, Si, 0.644; S, 0.089 ; while one analysis under dolomite gives Si, 0.508 ; S, 0.070. For No. 2 iron, the limestone flux gives, as an average of 19 analyses, Si, 1.107; S, 0.051; while the average of 4 analyses made with dolomite flux gives Si, 0.630; S, 0.056. It will be observed, that no No. 1 pig is given under limestone, while 14 analyses appear under dolomite, averaging Si, 0.950 ; S, 0.028. As nothing is said about changed conditions, it is Fair to presume that the ore and fuel, as well as the blast-temperature (which is stated to have been uniform at about 750' F.) remained practically the same; and since the sulphur in the two fluxes is not given, it is impossible to know whether the lower sulphur for equal silicon-contents is due to the use of dolomite or to other conditions. The use of dolomite would produce a more fusible cinder, and the furnace would be hotter than when using limestone; therefore, we might expect to see a grayer iron. The amount of So. 1 iron made with dolomite seems to confirm this supposition; and, under these conditions, we might expect more of the sulphur to be volatilized, and to pass off in the gases. The easier fusibility of the cinder would also permit more rapid driving; and this should reduce the amount of silicon and sulphur in the iron, as the amount of reduced metalloids in the pig is directly proportional to the length of time it remains in the reducing-zone.

Jan 1, 1895

By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948

By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948

By R. W. Smith, Z. Sadowski

The stabilities of finely divided mineral suspensions were determined as functions of pH and concentrations of polyethylene oxide, sodium ligninsulfonate, sodium dodecybulfate, and sodium oleate. In addition, the electrokinetic potentials of the minerals were determined under identical pH and additive concentration conditions. Flocculation or dispersion of the suspensions is discussed in terms of both the amount and manner of adsorption at the appropriate solid-liquid interface as it is influenced by additive concentration and pH.

Jan 1, 1986

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By E. T. Wessel

UNEXPECTED brittle failures of metals in practical applications are a serious problem to many industries and to the nation as a whole. Considerable effort has been devoted to studies of the brittle behavior in metals. However, the major portion of this effort has been directed at developing techniques and apparatus for the purposes of determining the susceptibility of metals to brittle failure and of making various types of observations of the phenomena. Relatively minor effort has been made to understand the basic mechanisms involved in initiating brittle failures. A more complete understanding of the nature and mechanism of the brittle failure problem would be very helpful in efforts directed toward predicting and avoiding brittle failure and toward the development of suitable materials and designs that are not susceptible to a brittle behavior. The intent of the present investigation is to acquire this basic understanding. The pronounced transition from a ductile-to-brittle behavior is most prevalent in metals having the body-centered-cubic lattice structure, primarily be- cause metals of this structure exhibit a strong dependence of yield strength upon temperature and the rate of straining. The generally recognized qualitative concept of the ductile-to-brittle transition is that brittle (cleavage) failure occurs when the yield strength exceeds the cleavage fracture strength. This condition can apparently be achieved by decreasing temperature or increasing strain rate. Likewise, a normally ductile metal can be made to fracture in an apparently brittle manner by the introduction of triaxial stresses (notches) where the ratio of normal to shear stresses can be increased to such an extent that the normal stress exceeds the fracture strength before the critical shear stress for plastic flow is achieved. Neither of these concepts require any prior plastic deformation or explain why the observed fracture strengths are so much less than the theoretical cohesive strength. The results of several investigations of the ductile-to-brittle transition in body-centered-cubic metals illustrate rather conclusively that measurable amounts of nonelastic deformation do precede cleavage fracture, even at extremely low temperatures. These studies suggested that the early stages of plastic flow, particularly abrupt yielding, and their relationship to brittle fracture should be examined

Jan 1, 1958

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966

By A. Goldberg, T. E. Tietz, J. E. Dorn

Introduction The concept that the flow stress for plastic deformation of metals in the work hardening range is a function of the instantaneous values of the strain, strain rate and test temperature was promulgated by Ludwick' many years ago. This thought has been more or less a guiding principle throughout the immediate period of development and growth of mechanical metallurgy. It has been tacitly assumed or knowingly applied to many investigations on the plastic behavior of metals. Spurred by the theoretical interest and practical importance of the plastic behavior of metals, many investigators have attempted to determine empirical, semi-empirical, and theoretical equations2-l8 relating the flow stress with the strain, strain rate, and temperature. Although the applications of such equations have been extensive, the experimental verification of the existence of a mechanical equation of state is weak. Furthermore, some of the available evidence on plastic flow appears to suggest that no simple functional relation between stress, strain-rate, strain and temperature can exist. The mechanical equation of state demands that Where a = true stress = loadlinstantaneous area e = true strain _ Instantaneous gauge length ~ initial gauge length i = true strain rate T = temperature This formulation implies that da is an exact differential. Therefore the flow stress (a) is a function of the instantaneous values of the strain (c) the strain rate (i) and the temperature (T), independent of the previous mechanical or thermal history. Having reached a certain strain, strain rate, and temperature, by any path whatsoever, a definite and fixed value of the flow stress should be obtained. One check on the validity of the mechanical equation of state is easily obtained. Consider the following three tests on the stress-strain curve at constant temperature: A. Strain at rate :I B. Strain at rate it C. Strain at rate 11 to el and continue test at &. A graphical representation of possible results of such tests are shown in Fig I. If, for strains greater than el, test (C) data coincide exactly with the data from test (B), as shown in Fig ra, a limited verification of the mechanical equation of state is obtained for the range of strain rates from il to iz. But if the data from test (C) differ from those of (g) beyond strain t\ where the strain rate is changed from il to k2, the mechanical equation of state is not

Jan 1, 1949

By P. van Meurs

This paper describes a technique which permits visual observation of oil displacement processes througlrout the interior of a porous structure as thick as 2 in. A model having glass walls is filled with finely powdered glass. Such a model becomes completely transparent if the powdered glass pack is saturated with an oil having the same refractive index as the glass. When water or gar, with a refractive index different from that of the oil (glass) is injected, the model becomes opaque in the space occupied by the water (gar). visual observation and photography of these displacement processes are thus rendered possible. The following processes have been studied: (I) displacement of oil by water (linear drive) in a homo-geneous formation and in a stratified formation, (2) water flooding (five-spot well pattern), (3) solution gas-drive process, and (4) oil-bank formation. INTRODUCTION Most of the scaled model experiments heretofore carried out in the Koninklijke/Shell Laboratorium, Amsterdam, have been done in steel containers, in which oil-saturated sand packs represented the oil-bearing formation. In such experiments, for instance those on the displacement of oil by water, the cumulative oil production was measured as a function of the cumulative water injection. In order to interpret the measured production data, a need has for some time been felt for a means of observing visually what happens in the course of such experiments. Some information of this kind was obtained earlier by observing the water-oil distribution in various cross sections of the sand after the conclusion of the experiment.' However, the technique used did not guarantee that the fluid distribution remained undisturbed. Moreover, the procedure was somewhat elaborate and the information obtained limited. Therefore a new technique has been developed, which is described below. DESCRIPTION OF EXPERIMENTAL TECHNIQUE AND APPARATUS Glass models simulating part of an oil reservoir are filled with ground Pyrex glass of a specific grain size, representing the porous structure of the prototype. Before an experiment is started, the porous formation has to be saturated completely with an oil having exactly the same refractive index as the Pyrex glass powder. All light-scattering surfaces of the glass grains become invisible and the formation is then transparent. If the oil is displaced by another fluid (e.g. by water in a water-drive experiment, or by gas liberated from the oil in a solution gas-drive experiment) the formation becomes opaque in the region where the oil is expelled from the rock.* The back of the apparatus is painted black and illumination is from the front; therefore, in the photographs of the experiments, the oil-bearing formation appears black, whereas the water- or gas-invaded areas are white.

Jan 1, 1958

By A. M. Abouzeid, S. Chander, D. W. Fuerstenau

Today numerous ores contain valuable minerals in finely disseminated form; and although the recovery of these fine mineral particles is generally exceedingly difficult, diminishing raw material resources necessitates the recovery of such mineral values. In many systems, the efficiency of recovering fine particles is still extremely low and often fine particles must be discarded as slimes. However, in recent years, various advances have taken place in the recovery of mineral particles in the very fine size range. In this paper, the background and performance of a number of processes for fine particle processing and separation are reviewed and discussed, particularly from the point of view of how fine particle recovery might be improved.

Jan 1, 1979

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949

By Wallace Ralston

DuRing the year of 1937, the East Texas district produced 211,194,467 hbl. of oil and marketed more than 22,329 million cu. ft. of gas; 3377 oil and gas wells were completed. During this same period 106 exploratory wells were drilled, discovering three new oil fields and one gas-distillate field. Fields East Texas Field.—The East Texas field again led the district as to production and number of wells completed. During the year, 2420 oil wells were completed, making a total of 24,382 producing wells, which produced 171,336,854 bbl. of oil, for a total of 1,156,352,834 bbl. since the beginning. During the year the average bottom-hole pressure dropped 49 lb., making the average bottom-hole pressure 1119 lb. Approximately 3500 wells are making salt water, 20 per cent of them making over 80 per cent of the water. During the month of December, the daily average production of salt water was 119,000 barrels. Talco Field, Titus and Franklin Counties.—The Talco field produced 9,780,948 bbl. of oil during the year, from 637 wells. During the year 472 wells were completed. All of the wells are pumping and 241 are making salt water. This field has followed a normal development and did not exceed the estimated number of acres reported last year. Rodessa Field, Cuss and Marion Counties.—The Rodessa field was extended about 13 miles southwest into Marion County, which added approximately 4000 acres to the field. During the year 260 wells were completed, making a total of 416 producing wells, which produced 12,646,-970 bbl. of oil. The author was unable to obtain figures for the amount of gas produced. The field has two gasoline plants, which had a daily average of 16,558,000 cu. ft. of gas during December, averaging 0.83 gal. per M cu. ft. As of Jan. 1, 31 wells were making salt water. The bottom-hole pressure varies greatly, depending upon the pay from which the well is producing. The average bottom-hole pressure from the Young

Jan 1, 1938

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By R. J. Keene

The South Works high-tonnage billet caster was started in late March 1971, with the first heat being successfully cast to completion. Currently, over 31,500 tons per month are being produced. U. S. Steel designed and built this caster with the objective of producing quality-steel billets for critical bar, rod, and wire applications. The essential design parameters were based on studies conducted on the Research Laboratory's pilot caster, also located at South works. 1,2,3)* The caster is a four-strand, straight-mold machine that produces 7.5-inch- square billets at rates exceeding 300 tons per hour. An in-line-reduction mill reduces each strand to either 6-inch-, 5-inch-, or 4-inch-square billets.

Jan 1, 1972