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By C. H. P. Lupis, R. Hocine, G. Bernard

The necessary and sufficient conditions for the stability of a multicomponent phase with respect to infinitesinzal fluctuations are derived and transformed to be written in terms of activity coeffcients and mole fractions rather than in terms of the customary second deritlatives of the free energy. NECESSARY conditions for the stability of a multi-component system were derived by Gibbs as early as 1876.' However, as the usefulness of these conditions is greatly enhanced by the simplicity of their translation in terms of functions of common usage, the present contribution establishes these conditions in terms of activities or activity coefficients-and mole fractions. It was shown in another article2 that not only may these conditions be used for the prediction of the appearance of new phases, but they may also provide a check on the orders of magnitude of the interaction coefficients involved. "Spinodal" decomposition is said to occur when, at constant temperature and pressure, the system is unstable with respect to infinitesimal fluctuations in composition. As a result, the "phases" which appear may be attained through continuous changes in the system rather than discontinuous ones, and, consequently, the free energy of these phases may be described by a unique continuous free-energy function. For a binary system, the familiar curve of Fig. 1 illustrates the case we wish to extend to a multicom-ponent system. The conditions to be written pertain to the decomposition of a system of n moles into moles of phase moles of phase v, ...hen moles of phase 9, where the phases a, ...v, ...9 are—at least initially-arbitrarily close in composition to that of the original phase. Each A, is positive and since the total number of moles n in the system remains constant: Each phase v contains hv(nl +dnY) moles of component (I), ...xV(ni +dny) of component + dnk) moles of component (m). The total number of moles ni in the system remaining also constant, it is clear that:

Jan 1, 1968

By G. Y. Chin, M. T. Dolan, W. L. Mammel

The least work analysis of constrained deformation, first proposed by Taylor and recently modified by Chin, Hosford, and Mendorf to include twinning, has been applied to the problem of axisynmetric flow. Calculations were made, for the case of (111}(110) slip and {111}(112) twinning applicable to fcc deformation. The solutions were obtained by linear programming techniques and with the aid of computer methods. The results show that in axisymnzetric tension the onset of twinning tends to decrease the plastic strength anisotropy as compared with the case of defortnation by slip alone. In compression, however, the strength anisotropy is increased as a result of twinning. The [100] and 11111 orientations and their vicinity are unfavorable for twinning in tension and compression, respecticely. With slight modifications, the present results may be applied to bcc metals deform ing by {110}(111j slip and (112} (111) twinning. Implications of present results to wire texture development of low stacking fault energy fcc materials arc discussed. PREVIOUSLY we' have applied linear programming techniques to obtain solutions to Taylor's least work analysis2 of constrained deformation of single crystals undergoing axisymmetric flow, such as occurs in an axially loaded polycrystalline aggregate. These solutions yielded values of the parameter M = o/.r = Y/w which relates the external stress-strain (u-c) curve to the shear stress-shear strain (7-y) curve for the crystal. The value of M is dependent on crystal orientation and hence enters significantly in texture strengthening considerations.3'4 Recently the Taylor hypothesis was modified by Chin, Hosford, and Mendorf' to include mechanical twinning. The latter has now been applied to the problem of axisymmetric flow and the results are reported in this paper. Calculations have been made for {111 )( 110) slip and {111 )(112) twinning applicable to fcc crystals. With minor changes in the indices of the slip and twin systems, the present results are also applicable to bcc crystals which slip on (110) (111) and twin on {112)(111) systems.

Jan 1, 1970

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By M. E. V. Plummer, F. E. Beamish, J. C. Hole, J. M. Kavanagh

Prior researches have shown that the iron-copper-nickel content of platinum concentrates may be reduced by carbon to form a collecting alloy for the platinum metals in a manner exactly analogous to the formation of the lead fire assay button. The nature of the iron-copper-nickel alloys with the platinum metals has been investigated. Palladium and probably some of the other platinum metals form solid solutions with this alloy. ONE of the greatest known reserves of the platinum metals is to be found in the nickel, copper, iron sulphide deposits of Northern Ontario. The very large tonnage of copper-nickel ore processed makes the Sudbury district a significant world source of the platinum metals, the latter being recovered as byproducts in the electrolytic refining process for copper and nickel. Chalcopyrite, pentlandite, and pyrrhotite are carriers of the platinum metals;' these minerals contain from 0.03 to 2.0 ppm of the noble metals. The analysis of the above ores for the platinum metals necessitates an initial concentration of the minute quantities present in the ore. The method usually employed involves the extraction of the noble metals by molten lead with or without small proportions of silver. The lead is then separated from the precious metals by cupellation, a process which involves absorption by the cupel and volatilization of lead oxide, leaving the precious metals collected in a silver bead on the surface of the cupel. The collection by lead is probably achieved by a process of dissolution followed by some degree of segregation in the lead alloy since the cold button is seldom uniform in composition. With silver-lead alloys this process of liquation has been used to re- cover pure lead since, during the cooling period, crystals of pure lead separate and silver becomes concentrated toward the center of the solid.' Platinum and gold liquate in a manner similar to silver which may account for the successful recovery of platinum by fire assay even though it is considered insoluble in a solid lead medium. 3 In the case of iridium the liquation process may be a disadvantage in that the iridium may appear in the outer areas of the button and thus be lost mechanically during the handling processes. In any case the deficient alloying characteristics of lead for the platinum metals encouraged attempts to find an improved collecting alloy, and by analogy with aqueous extractions, preferably one in which solid solutions would be readily formed. Since, beyond a certain minimum solute to solvent ratio, the formation of a solid solution is accompanied by a lattice distortion, one would expect some relationship between the atomic diameters of any two metals and their tendency to form a solid solution. In one survey5 the hypothesis was put forward that when the atomic diameter of the solute differs by more than about 15 pct from the solvent, the "size factor" is unfavorable and the formation of a solid solution is restricted. On the other hand, when the atomic diameters are within this limit the size factor is favorable and solid solutions are readily formed, e.g. the transition metals of Group VIII having similar radii form solid solutions over wide ranges of composition.6 Even with a favorable size factor, elements having different crystal structures cannot form a continuous series of solid solutions. Cell dimensions alter as the concentration of the solute increases, causing a

Jan 1, 1962

By E. Brunner, E. S. Mardock

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By E. S. Mardock, E. Brunner

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By L. K. Borrett ond C. S. Yusi

The authors have made extensive use of a modern field of mathematics, topology, to give a new approach to the study of sintering. They present a topological model for the sinter body and the void space, and establish a relationship between them. However, in an interdisciplinary paper of this nature it is important that the material be presented, insofar as possible, in

Jan 1, 1967

By Alan T. Gorton, T. L. Joseph, Gust Bitsianes

High-temperature X-ray diffraction techniques were used to determine thermal expansion coefficients of iron and its oxides. Lattice parameters of a and iron, wiistite, magnetite, hematite, and goethite were determined and plotted as a function of temperature. From these results, the true and mean linear thermal expansion coefficients were calculated. In the case of noncubic crystals, the expansion coefficients were determined along each of the crystallographic axes. The effect of the magnetic transformation on lattice parameter was measured for a iron and magnetite at their respective curie temperatures. COEFFICIENTS of expansion for iron and its oxides were determined from the temperature dependence of their lattice parameters. From these data, the true linear coefficients were derived by means of the formula: at =[(l/ao )(dao/dt)] [1] where at is the true linear coefficient of expansion, a, is the lattice parameter in angstrom units, and all variables are referred to the temperature, t, in OC. Thus the true expansion coefficient represents the instantaneous change in lattice parameter on a unit basis and at a particular temperature. A second expansion coefficient is also often used. It is termed the mean linear coefficient and is defined in the following way: am = [ao(t) - ao(O)]/ao(0) l [21 This coefficient represents the average change in lattice parameter on a unit basis but at a specified parameter length, ao at O°C, and over a specified temperature range,1 to 0°C. Generally the true co-

Jan 1, 1965

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 J. B. Dilworth

In estimating the investment-value of a mining-property or plant, the value of which decreases with operation, it is often necessary to know the sum which must be set aside periodically from earnings either to renew the plant at the end of its life, or to return the capital involved when the earningpower of the investment has ceased. In such cases it is manifestly incorrect simply to divide the total amount to be retired by the 'number of periods (usually years) during which the investment shall be active, as the sums periodically withdrawn have a certain interest-earning power varying with the length of time they are held and with the opportunities afforded for their investment. But though the interest may be considered to accumulate regularly year by year, yet the rules and tables for compouiid interest do not apply, owing to the addition of a fixed amount of new money to the total at the beginning of each period. Briefly stated, the problem of sinking-funds is, to find the amount of money which must be periodically set aside at a certain rate of interest, regularly compounded, to yield a certain sum in a given length of time. In most practical cases the interest is compounded and the fresh amount added at the same time—usually once a year—and on this basis the problem may be solved as follows : Let S = total amount to be retired, Let T = interest rate : R = 1 + r, Let n = life of tlie sinking-fund or the amortization-period, Let L = the sum set aside at the end of each year. Then the amouilt of the sinking-fund at the end of first year is 2, which at the end of n years will have illcreased by compound interest to IRn-l. Similarly, another amount, x, will be set aside at the end of second year, which will in turn increase

Jan 1, 1911

By W. R. Toeplitz

H. N. Ghenn.*—It has been established that the accuracy obtainable from any precision machine is a function of the wear resistance, maintenance and closeness of fit of the bearings, hence I would like to ask Mr. Toeplitz how these oil-less bearings compare with cast iron or babbitt or similar materials when used on precision machinery. Could these bearings be used, for example, on a grinding machine in which work must be held to a tolerance of plus or minus 0.000025 inch? W. R. TOEPLITZ.—The metal-powder bearings can be held to very close tolerances and are used in place of cast iron and babbitt on precision machinery.

Jan 1, 1945

By H. M. Howe

The chief purpose of this note is to call attention to the triaxial diagram as a convenient means of illustrating the properties of slags, and by this example of its use to commend it to those inclined to graphical studies having other possible applications. Explanation.—In the common or di-axial diagram, the properties corresponding to any point are determined by its perpendicular distance from each of two axes. For example, in an ordinary stress-strain diagram the properties of a given point in the curve are, first, a stress cd so many pounds per square inch, because its perpendicular distance from the horizontal axis of the diagram corresponds by the vertical scale to that stress; and second, a strain or elongation of so many per cent., because its perpendicular distance from the vertical axis corresponds by the horizontal scale to that elongation. It happens that, as a matter of convenience, we habitually place these two axes at right angles to each other; so that our measurenieilts happen to be made not only at right-angles to

Jan 1, 1899

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By F. Weinberg, L. MacAulay

DAVIS,' in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"', was determined with the

Jan 1, 1970

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios were obtained for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in natural gas-condensate systems. Two different overall mixture compositions were investigated over the pressure range 500 to 4,000 psia at 100°, 150°, and 200 °F. Partial phase diagrams of the mixtures were obtained; one of these showed a critical point at 204°F and 3,875 psia. These and earlier data' were compared with the Kellogg correlation' at! 100°F and 1,000 psia. INTRODUCTION The authors' have presented equilibrium vaporization ratios for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in complex mixtures, such as natural gas-crude oil and natural gas-absorber oil. Since mixtures of the natural gas-condensate type also occur widely in petroleum reservoirs and often contain the non-hydrocarbons mentioned, it would be useful to have appropriate K data for calculating equilibrium vaporization conditions. Roland, Smith, and Kave-ler' obtained K's for methane and the light hydrocarbons in gas-condensate mixtures; and Poettmann and Katz3 obtained K's for carbon dioxide in a gas-condensate system. The data presented in this paper extend this coverage to include K's for nitrogen and hydrogen sulfide and phase diagrams for the experimental mixtures. EXPERIMENTAL WORK The equipment and experimental procedure was essentially as described previously, except for analysis of the vapor samples. The vapor sample bombs were filled at the pressure and temperature of the run. Immediately after sampling, a portion of this sample was flushed from the bomb into a 650 cc glass bulb, filling it to near atmospheric pressure. The sample in the glass bulb was then analyzed by the mass spectrometer. Some checks were made on this analytical procedure to find the accuracy of measurement of the C + content of the vapor samples. The modifications tried were complete fractionation of the vapor sample and the use of several liquids (depropanized condensate and retrograde liquid from several vapor samples) as calibrating materials for the mass spectrometer. The results obtained from these various checks differed by about 10 per cent relative and this is believed to be the order of accuracy of the vapor C+ concentrations.

Jan 1, 1953

J. K. EVELETH, Anaconda, Montana (Communication to the Secretary): Partly for the reasons which Mr. Jones enumerates, and partly because of the presence of copper in greater or less quantities in so large a proportion of the ores throughout this region, I have also found Marguerite's method the most convenient and satisfactory for the determination of iron. In order to avoid the previous precipitation of the copper with H2S on the separation of the iron by means of ammonia, with the consequent necessity for re-precipitation

Jan 1, 1889

By M. Stern, I. S. Servi, W. W. Webb

ZINC has been considered an ideal material for investigations of the behavior of dislocation walls in metals. It has appeared particularly useful for studies of the mechanisms of plastic deformation and the motion of low-angle boundaries under stress, because orientated crystals are easily grown and cleaved. Moreover, the hexagonal structure makes the introduction of controlled tilt boundaries relatively simple. Apparently, another of the many reasons for selecting zinc as a working material is its commercial availability at the 99.999' pct purity level. However, most elements are only slightly sol-

Jan 1, 1959

By I. R. Kramer

The apparent activation energy, U, JOY plastic deformation of aluminium, copper, and gold single crystals and polycrystalline aluminum was found to he dependent upon surface condition. At low strains, the value for U for aluminum single crystals was 4200 cal per mole ; however, this value decreased to 920 cal per mole when the specimens were polished during the test at a rate of 50 X 10-5 win-1 The activated volume also was found to increase with the rate of metal removal. That the surface plays an important role in plastic-deformation processes has been adequately demonstrated.1-4 Of particular interest at this time are the observations4 that the creep rate of single crystals of fee metals is increased markedly when specimens are polished during the deformation process. These observations were interpreted in terms of a dislocation debris layer at the surface regions of the crystal. This layer, which appears to be a region containing a high concentration of dislocations or segments of dislocations, not only will impede the egress of dislocations on the primary slip system, but will also provide a barrier against which dislocations may pile up. By this means, a stress which opposes the motion of dislocations will be generated. It is considered that this stress must be taken into account in any theory which describes the plastic-deformation process. Although a detailed dislocation model cannot be given at this time, it may be stated that the stresses opposing the motion of dislocations arise from the dislocations in the debris layer, Ts, and ti due to the resistance to motion imposed by internal obstacles such as Lomer-Cottrell barriers, subgrain and grain boundaries, forest dislocations, and so forth, as well as the resistance due to the presence of jogs on dislocations and the interaction of the stress fields of dislocations, and so forth. In essence, we have added an additional term, ts, to the usual form of the equation T = Ta- Tb, where Tb is the back stress due to the various types of obstacles which impede the motion of dislocation. Accordingly, the net stress, t, acting on a dislocation may be written as where Ta is the applied shear stress. For deformation which occurs by a thermally activated process5,8 ?=Ae-u/kT = A e(u,-VT)/kT [2] and U = Uo- Vt PI where U = activation energy for plastic flow, y = shear strain rate, Uo = activated energy for plastic deformation in the absence of stress and depends upon the particular deformation process, V = activated volume, k = Boltzmann constant, T = temperature, OK, and A = frequency factor. From Eqs. [I] and [3], U = Uo- V(Ta - Ti - TS) [4] and it is seen that if Ts decreases, the activation energy, U, must decrease if V remains constant. However, as will be shown, V is a function of the surface conditions. In their work on aluminum, Lytton and coworkers7 reported that at low strains the activation energy was 3400 cal per mole and at high strains it was 28,000 cal per mole. The lower value was interpreted in terms of the energy necessary to overcome the Peierls force, while the higher value was associated with the energy necessary for dislocations to move by a cross-slip process. It will be shown that the lower activation energy is associated with the surface debris layer rather than with the Peierls force. EXPERIMENTAL PROCEDURE Single crystals having a nominal cross section of 1/8 in. and a 3-in. gage length were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The initial purity of the metals was 99.997, 99.999, and 99.999 pet for aluminum, copper, and gold, respectively. The orientation of the specimens is given in Fig. 1. The measurement of the activation energy as a

Jan 1, 1964

By H. D. Hoskold

DuRing the last few years, various persons have been put forward as originators of some mechanical device for the purpose of finding distances without the use of a chain or other linear measuring-instrument, and among these, the Englishman, Gascoigne, 1639, is prominent as the first in England; while James Watt, 1771, and William Green, 1778, are also included in the list of inventors. It is possible that this useful and important problem occupied the attention of others prior to the date cited, and, consequently, it is difficult to decide what nation first gave birth to the inventor of an instrument for the object under consideration. A very important work appeared, not long since, in Paris, devoted to a history and discussion of some of the older and newest forms of surveying-instruments,* and at page 79 of that work a curious old instrument is exhibited, called Bigonometre, i. e., an instrument for finding distances and solving trigonometrical problems. in surveying. A copy of the diagram of the instrument exhibited in the book referred to is represented in Fig. 1. Having had an occasion to read the French work referred to, I communicated with the author of it, and he was good enough to reply that he found a diagram of this old instrument in a book published in 1597, by Danfrie, existing in the library of the Academy of Sciences, in Paris. Col. Laus-

Jan 1, 1904