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By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick's first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank' supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains' Glasstone, et al' treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity' has shown how to convert the Onsager equations to a form very similar to Lamm's. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By Werner Langguth

SINCE the introduction of the improved method of precipitating gold from chlorine solution by SO2 and H2S at the Golden Reward chlorination-works, Deadwood, S. D.,* this modern method has been further adopted in the chlorination-works of the Portland Consolidated Company at Deadwood, and in those of the Black Hills Milling and Smelting Company at Rapid City, S. D. It has proved practically most successful in the handling of large quantities of gold solution, and constitutes up to date, with Mr. John E. Rothwell&apos;s most important improvement, namely, barrel-leaching under hydraulic pressure, the principal progress made in gold chlorination. The method of refining the gold sulphides which result from this method of precipitation, was introduced by me in 1890 at the Golden Reward works, and in 1892 at those of the Black Hills Company. It has not suffered any changes during the last three years, and is substantially as described below:

Jan 1, 1895

By Samuel E. Doak

The utilization of rotary kilns, of the well-known cement type, for the preparation of iron ores for the blast furnace, has become of considerable economic importance within the past 10 years in certain localities, notably those where the native ores are lean. Such kilns may be used simply for the agglomeration of ores too fine to be charged into the blast furnace (i.e., ores whose, loss in the dust catchers is excessive, and whose fineness is detrimental to the working of the furnace), or for the desulphurization of lump and fine ores the sulphur content of which does not exceed 6 or 7 per cent. The desulphurizing action can be combined with that of agglomeration provided the kiln is sufficiently large. Other processes have been developed for the same purpose, but while I am not able to draw a comparison between them by reason of lack of sufficient data, it is safe to say that the kiln, if properly dimensioned for the character of ore to be treated, will compare favorably in its results, both as to economy and quality of product, with any other process. It is not, however, as well adapted for the treatment of flue dust as is a sintering operation, on account of the large percentage of fine coke contained therein. Any combustible entering the kiln at its feed end renders the process very much more expensive and unsatisfactory on account of the difficulty of controlling the temperature, also because of the rapidity with which long "rings" form, due to the increased heat at the cooler end of the kiln. The greatest value of the kiln at present is in the treatment of pyrites cinder; that is, the residue from pyrites ore after the extraction of the greater part of the sulphur. This cinder, while high in iron content, has too much sulphur remaining in it to be allowed to form a large part of the blast-furnace burden, without further treatment. It will range in metallic iron from 42 per cent., representing a very low-grade cinder from a domestic pyrites, to 64 per cent. of the residue from the best Spanish ore, and the corresponding silica content will vary from the maximum of about 25 per cent. to 11/2 per cent. The residual sulphur depends largely on the type of burner used in the original desulphurization. In general, the leanest original ores retain the greatest amounts of sulphur. In modern practice the percentage of sulphur in the cinder is rarely as great as six, and seldom lower than one and one-half. Average analyses for iron, silica, and sulphur of the cinders that have come under my personal observation are as follows:

Jan 1, 1916

The University of Illinois, by Prof. H. H. Stock, professor of mining engineering, sent out to its mining students a long letter urging them to attend a Chicago meeting of the Institute. It stated that the University Council authorized the remission of the registration fee for sophomore, junior and senior mining engineers who would attend the meetings and present a written account of the sessions and excursions attended. Young engineers are rarely flushed at the beginning of their careers but if they ever expect to amount to anything at the end of 10-years-they are going to regret that they have not long been a member of the Insti-tute. So that the slogan "Do it now" is snore than particularly appli-cable in their cases and nothing will better indicate to them the scope of the Institute&apos;s work and the advantages which they are to get from mem-bership than attendance at one of the big meetings of the Institute and the preparation of a written report on the sessions and excursions attended to be returned to the University.

Jan 11, 1919

By Roswell Johnson

To know the rate of decline of oil wells is very important, yet ordinarily we are prevented from getting this rate because the oil from several wells is put into one or a few tanks as soon as the wells have been connected to the power. The object of doing this is economy of tanks, pipes, labor and accounting. FIG. 1. But we are making a great sacrifice for this small economy. The advantages of the individual records are that we would know better: 1. When the well has ceased to be profitable. 2. When a well has gotten into bad condition. 3. The real record of the yield per acre and the rate of decline of the wells. The lease total is too mixed as to age of the wells for existing records to have much significance. To obtain such individual well records and more accurate logs are the great desiderata of satisfactory management of oil properties. 4. Which wells show the slowest decline-information which is valuable in locating new wells or purchasing adjoining leases.

Jan 6, 1917

By V. Koump, R. H. Tien, W. J. Kim

This paper presents an approximate solution of the problem of freezing of a binary alloy. he alloy is in the form of a one-dimensional slab of finite thickness. The surface temperature of the slab is assumed to be constant and lower than the solidus (or eutectic) temperature. The densities of the liquid and the solid are assumed to be equal. For a given binary alloy system, initial concentration of solute and surface temperature, the solution yields a) the temperature distribution in the solid skin, b) the temperature, concentration, and solid fraction distribution within the solid-liquid region, and c) the positions of the liquidus and the solidus (or eutectic) fronts as a function of time. The results of calculation for Fe-C and Fe-P systems are presented. In this investigation we are considering the problem of solidification of a binary alloy. The alloy is in the form of a one-dimensional slab of finite thickness. The molten alloy is initially at liquidus temperature. At time zero the surface of the slab is reduced to a temperature T, < Te,, where Te, is the solidus (or eutectic) temperature and T, is a constant. The densities of solid and liquid alloys are assumed to be equal and independent of temperature and composition. A qualitative picture of solidification of an alloy, under these conditions, is illustrated in Fig. 1. During the initial stage of solidification, before liquidus front reaches the center of the slab, freezing proceeds by propagation of two isothermal fronts, the liquidus front and the solidus (or eutectic) front. The fraction of solid at the liquidus front is zero; the fraction of solid at the solidus front is unity, The solid fraction and the temperature distribution between the two fronts and the width of the solid-liquid region change with time. During the later stage of freezing, after the liquidus front reaches the center of the slab, the liquidus front disappears. The solid fraction and the temperature at the center of the slab, as well as throughout the solid-liquid region, are now changing with time. The solidification is completed when the fraction of solid at the center of the slab reaches unity. In solution of this problem we seek to determine a) the temperature distribution in the solid, b) temperature, concentration,

Jan 1, 1968

By C. R. Fettke, Bela Hubbard

During the summer of 1916, while on a visit to the United States Agricultural Experiment Station at Mayaguez, Porto Rico, the writers were told by D. W. May, the director, that an occurrence of manganese ore had been reported from the mesa southeast of Mayaguez. A visit to the locality showed that the mesa is covered by a mantle of bright red soil resting upon serpentine. Here and there over its surface concretionary masses of limonite have been mashed out of this soil. These were apparently mistaken for manganese ore. On account of the similarity of this occurrence to the extensive iron deposits of northeastern Cuba, it was thought that a brief description based upon a two days&apos;reconnaissance survey of the area mould be of scientific interest. Mayaguez is on the west coast of Porto Rico, at Mayaguez Bay, which is the third in importance of the harbors of the island. The city itself is about 3/4 mile inland on the low-lying plain at the mouth of the

Jan 1, 1920

By Chas Fettke

DURING the summer of 1916, while on a visit to the United States Agricultural Experiment Station at Mayaguez, Porto Rico, the writers were told by D. W. May, the director, that an occurrence of manganese ore had been reported from the mesa southeast of Mayaguez. A visit to the locality showed that the mesa is covered by a mantle of bright red soil resting upon serpentine. Here and there over its surface concretionary masses of limonite have been washed out of this soil. These were FIG. I.-MAYAGUEZ FROM NORTHWEST END OF MESA. apparently mistaken for manganese ore. On account of the similarity of this occurrence to the extensive iron deposits of northeastern Cuba, it was thought that a brief description based upon a two days&apos; reconnaissance survey of the area would be of scientific interest. Mayaguez is on the west coast of Porto Rico, at Mayaguez Bay, which is the third in importance of the harbors of the island. The city itself is about ¾ mile inland on the low-lying plain at the mouth of the

Jan 3, 1918

By P. C. Hodges

WHILE there is very little romance connected with the operation of a stone quarry, yet to those who have participated in the growth and development of a business that has been a pioneer in its field and that FIG. 1.-LOCATION OF PROPERTY OF MARBLE CLIFF QUARRIES COMPANY. has been in continual operation two-thirds of a century there is bound to be a background of experience, which if properly capitalized, brings progress as well as satisfaction in its accomplishment.

Jan 1, 1936

By A. C. Dorenfeld

CHANGES in circuits are often made in milling operations. At the same time that these changes are being evaluated the ores are changing. Even from the same mine, the ore is usually variable as to amount and type of mineral content, degree of association of valuable and gangue minerals, amount and types of soluble salts, hardness, etc. The question then arises whether any small differences in results, after changes have been made in the various circuits, are really due to these changes or whether the variability of the ore can account for those differences. Statistical evaluation provides one method of answering the question that arises so often in beneficiation studies: Did changed results come about because of changed process, or did ore variation cause the change? In this case, data were available for statistical analysis from an operating period of 42 months, representing treatment of approximately 1 million tons of ore. During this period there had been two flowsheet changes: 1) regrind of the zinc circuit middlings was introduced, and 2) alcohol- pine oil frother mixture was substituted for cresylic acid-pine oil frother mixture. Findings are in Table I.

Jan 10, 1954

By R. L. Templin

THE increasing use of aluminum and its alloys in commercial fields has demanded a better understanding of their machining properties. This fact is exemplified by problems that have arisen in the automotive and airplane industries, but many in other fields might be cited. As pure aluminum and its alloys in their various commercial conditions show appreciable differences in their machining properties, it is not surprising that quite divergent solutions have been offered for the machining problems encountered. However, if the fundamental requirements of the most suitable cutting tools for these metals are understood, these machining problems lend themselves more readily to satisfactory solutions. Since the machining of free cutting brass and mild steel is understood by most persons accustomed to working these metals, it may serve our purpose better to first make a general comparison of the tools more commonly used in machining these metals with the tools most suitable for machining aluminum, then proceed to a more specific discussion of the individual stools.

Jan 1, 1927

By Arthur Phillips

THE progress made in recent years in the art of dispersion-hardening has naturally led to an intensive study of alloy systems capable of yield-ing supersaturated solid solutions at ordinary temperatures. In general, the investigations have been confined to rather precise determinations of solubility limits and to experimental approaches designed to furnish more complete information regarding the rate and nature of precipitation under appropriate thermal conditions. Efforts are being made to focus more sharply on the atomic changes that are a direct consequence of the instability of the supersaturated solution. Here precision X-ray methods have come to be of considerable importance because lattice parameter measurements indicate very precisely the concentration of solute atoms in the solvent lattice. In spite of the general acceptance of parameter values as a criterion for the placing of solubility limits, it may be suggested that no thorough appraisal has been made of the several factors that conceivably may affect such measurements. More specifically, little attention has been devoted to the significance of surface energy conditions, specimen size and method of preparation, with par-ticular regard to the genesis of the grains and the surface concentration changes as a consequence of heat treatment and etching. Stenzel and Weerts1 recently published the results of a detailed study of precipitation reactions in aluminum-rich copper alloys. They found that, although copper lowers the lattice constant of aluminum, a 5 per cent copper alloy quenched from 150° and 225° C. had parameter values unquestionably higher than that of pure aluminum. Their results seem to substantiate, at least qualitatively, the earlier work of von Göler

Jan 1, 1934

By J. J. Gilman

IT is well established that dislocations exist in crystals and account for crystal plasticity.&apos; However, the origins of the dislocations are not clear. Among the means by which dislocations might originate are: a) through crystal growth accidents, b) by the collapse of condensed sheets of vacancies, or c) by stress-induced nucleation. Theoretical calculations&apos; have indicated that the last means should require very high stresses in order to operate. The purpose of this paper is to show that the stresses around the tips of cracks are large enough to nucleate large numbers of dislocation loops. Specifically, it will be shown that (100) cleavage cracks in LiF crystals nucleate dislocations in regions of the crystals where dislocations did not exist previously. It is believed that the use of LiF for this investigation does not restrict the significance of the 1 results. In fact, it is believed that this complements and extends previous papers by the same author which dealt with metal crystals.10,14 The dislocations were detected by means of the etching techniques that were described in a previous paper by Gilman and Johnston.3 In that paper it

Jan 1, 1958

By J. M. Dupouy, R. A. Rawe, M. B. Bever

The aging characteristics of a titanium alloy containing 13 pct V, I1 pct Cr, and 4 pct A1 have been investigated by hardness measurements, X-ray diffraction, and metallography. The P phase decomposes into 0 + a, and 0 + a, + TiCr, above about 1050°F; below this temperature a transition phase, believed to be w, precipitates first, followed by a, and TiCr,. The observed hardening is attributed to these reactions. Cold working of solution-treated specimens accelerates hardening and raises the hardness level attained. A TTT diagram is proposed. NEW titanium-base alloys, designated as "all-beta," have recently been developed. These alloys contain large amounts of P-stabilizing elements such as molybdenum, chromium, or vanadium. When cooled from the solution temperature, they consist only of P; in particular, the martensitic a,&apos; phase does not form.

Jan 1, 1961

By J. S. Levine, M. Prats

Several methods are available for calculating the performance of solution-gas-drive reservoirs from the PVT properties of the oil and from the relative permeability and other properties of the formation. These methods require a number of simplifying assumptions. The present method of computation has made use of a high-speed computer to solve simultaneously the nonlinear partial differential equations that describe two-phase flow by solution-gas drive in order to calculate the performance of a reservoir. Some of the results obtained by the nonlinear partial differential equation solution are compared with those obtained with an approximate method, which has been called the semisteady-state solution. The pressure and saturation profiles from the wellbore to outer boundary calculated by the two methods are compared for one constant-terminal-rate case and two constant-teminal-pressure cases. The agreement in these profiles, as well as in the values of average reservoir pressure and cumulative recovery, leads to the conclusion that, for most engineering calculations, the semisteady-state method will give a reasonable approximation to the numerical solution of the differential equations describing solution-gas drive. An unfavorable (as regards ultimate oil production) set of relative permeability curves was used in the calculations in the belief that the effect of the parameters which were studied would be emphasized to a greater degree. Furthermore, the reservoir was assumed to be completely homogeneous, and these results should not be considered applicable to any other type of reservoir. Gravity effects are not considered. The absolute permeability was varied from 25 to 0.5 md. At an economic limit of 2 B/D, the recovery for a 25-md reservoir is about 1.8 times as great as that for a 0.5-md reservoir. The effect of permeability on the producing gas-oil ratio is minor. Once PVT properties of the oil and the relative penneability properties of the reservoir are fixed, the pro- during gas-oil ratio is found to be a function of the fraction of oil recovered. Well spacings of 10, 40 and 80 acres were considered. For the assumed homogeneous-reservoir properties, the effect of spacing on recovery at an economic limit of 2 B/D was very slight. Certain dimensionless groups can be used to extend the results to other fields having different penneabilities, spacings, reservoir thicknesses, well radii and porosities, so long as the PVT and relative permeability properties are similar to those used in this paper. INTRODUCTION An important aspect of reservoir engineering is the prediction of the performance of the reservoir based on the limited information normally available early in the life of a field. Usually, soon after a field has been discovered, it is necessary to decide upon the spacing to be employed and the production program to be used for most efficient utilization of reservoir energy. Where these decisions have not been dictated by legal or political considerations, they have frequently been based on experience factors which indicate that two fields with similar characteristics will probably have similar performances. To the extent that the industry has been successful in economically exploiting oil reservoirs, this rule-of-thumb method has been found to have merit. A large amount of theory has been developed with which it is possible to predict the performance of a reservoir by using certain known properties of the oil and the formation. Because of the difficulties of the mathematics involved for a drainage area having square or rectangular boundaries, the problem usually has been simplified and idealized by assuming each drainage area to have radial symmetry and the field to be represented by a number of these drainage areas. Muskatl was one of the first to formulate the theory for two-phase flow and to solve the equations for a few cases by numerical integration, using the relatively slow means of computing available at that time. His equations describing

By G. E. Goodspeed

THE Cornucopia gold quartz veins form a parallel vein system traversing metamorphic and granodioritic rocks. Field and petrographic evidence suggests that metasomatism has played an important role both in the emplacement of the granodiorite and in the formation of the veins. Structurally the veins appear to be related to the major tectonic features of the Wallowa Mountains and to be narrow shear zones rather than filled fissures. Petrographic studies indicate a complex history of formation starting from initial alteration along fractures or joints followed by recurrent fracturing and a quartz-forming stage, and closing with continued shearing and microbrecciation, which permitted the upward percolation of the later ore- forming solutions. The precipitation of ore minerals from these solutions formed ore shoots. Postmineral effects include the injection of Tertiary basaltic dikes, a slight amount of cross faulting, and some movement along the planes of the veins as well as oxidation.

Jan 1, 1939

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

IN a search for an improved conductor for use in field wire for the L. S. Army Signal Corps, an alloy of copper and silver was developed from which it was possible to obtain 29 B & S ga. strands with tensile strengths in excess of 160,000 psi combined with an electrical conductivity of over 70 pct IACS. Such a favorable combination of strength and electrical conductivity has not been reported previously in the rather extensive literature covering this subject. The properties obtained from various binary alloys of copper and silver, together with the method of fabrication of these alloys which has been developed to obtain the properties desired in fine wire strands, are discussed in this paper. LITERATURE The effect on the electrical conductivity of copper of the various elements in solid solution is shown in Fig I, taken from published data by J. O. Linde and others.&apos; It will be noted that silver in solid solution depresses the electrical conductivity to a lesser extent than any other element for which data are given, and is followed rather closely by cadmium, and then by chromium. Zinc, which lies between cadmium and chromium, has so high a solid solubility in copper that the data for zinc are scarcely comparable to the data for the other two in the range covered. Not many data are available on the strain hardening of copper-rich Cu-Ag alloys. Corson2 reports a 3 pct Ag alloy properly cold worked and annealed to have 100,000 psi tensile strength and 90 pct IACS conductivity. On straight cold working, Hessenbruch3 reports 101.000 psi for a 5 pct Ag, 0.3 pct Be alloy, and 129,000 psi for a 30 pct Ag, 0.5 pct Be alloy. Here it would he expected that much of the strain hardening came from the silver content of the alloys. The copper-rich side of the Cu-Ag diagram, according to Stockdale,4 is shown in the upper part of Fig 2. The electrical conductivities for copper-silver alloys annealed at 750 and 350°C, taken from the work of Johansson and Linde,5 are shown in the lower part of Fig 2. The sloping line corresponds to the conductivity of solid solutions of silver in copper, and the horizontal offshoots correspond to the conductivity of the two-phase alloys in equilibrium at the two temperatures shown. The electrical conductivities are very high, even for the 750°C anneal. The potentiality for age hardening from supersaturated alpha copper solutions appears to be excellent from the solubility line, but Smith and Lindlief6 have shown that the response to age hardening of solution-annealed alpha alloys is not good. They found that the tensile strength of a 5 pct Ag alloy aged at various temperatures was not as great as in the quenched condition, even though, anomalously, the hardness increased from RB68 to RB78 by annealing for 4 hr at 400°C after a 750°C quench. Weist7 also found that the alloys increased in hardness

Jan 1, 1948

By Mark J. Klein

The precipitation of nitrogen in quenched and aged CY-35 at. pct Re was followed by internal-friction and electrical-resistivity measurements. It is shown that the precipitation kinetics of nitrogen from solution are many orders of magnitude lower in this alloy than in chromium. The reluctance of nitrogen to precipitate from sol~ction can be attributed to the composilional r-eadjustnzents required in the z.icinity of a chromium nitrade particle for gowth to occur. AS part of an investigation of the mechanism by which rhenium increases the low-temperature ductility of chromium and other Group VI-A metals, it was of interest to compare the concentration of interstitial elements retained in solution in chromium with that of a ductile Cr-Re alloy. The presence of certain interstitial elements in chromium has been shown to decrease its ductility1-5 and, of these interstitials, nitrogen is believed to have the most detrimental effect on mechanical properties. Thus, a comparison of the disposition of nitrogen in chromium with that in a ductile Cr-Re alloy might provide information about the mechanism whereby rhenium enhances the ductility of chromium. In previous internal-friction studies it was shown that the equilibrium solubilities of nitrogen in chromium and Cr-35 at. pct Re did not differ greatly.= However, results indicated that the actual concentration of nitrogen retained in solution at ambient temperatures is likely to be considerably greater in the alloy than in chromium because the precipitation kinetics of nitrogen are greatly retarded by the addition of rhenium. The objective of this investigation was to study the kinetics of nitrogen precipitation in Cr-35 at. pct Re in greater detail and to obtain information concerning the mechanism of nitrogen precipitation in this alloy. The properties studied were internal friction and

Jan 1, 1967

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934&apos; attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper&apos; by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949