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By L. G. Schulz, P. Spiegler

The electrical resistivity and the temperature coefficient of resistivity were measured with a potentiometric method using pure mercury as a reference material. Measurements were made nea,v roorn temperature. A detailed study was made of Hg,TI, near its melting temperature. THE work to be described was originally undertaken to provide the necessary data for interpreting the results of some optical experiments,' but because of the growing importance of liquid metals,273 it appeared that the results of the resistivity measurements should be published separately. For convenience the alloys selected were those which are liquid at room temperature. Special consideration was given to the Hg-T1 alloy closely corresponding to Hg,Tl, because recent X-ray diffraction results of Smallman and Frost seemed to show that the solid structure may persist to some extent into the 1iquid. EXPERIMENTAL PROCEDURE A potentiometric method was employed in which the resistivity of mercury was used as a reference. The essential features of the samples are shown in Fig. 1. A capillary tube CT with a bore of approximately 1.5 mm was fitted into two end cups, T, which were made of Teflon. A pair of current electrodes CE were immersed into the excess liquid metal which partly filled the end cups. The potential electrodes PE were inserted into CT through short pieces N of a no. 18 hypodermic needle held in place with Saureisen cement SC. As shown, the lower ends of the PE7s were reduced in diameter to 0.25 mm to minimize the distortion of the liquid metal cross section. Several methods were used to insert an alloy into the sample, but the usual one with mercury alloys was to fill the sample container with a weighed quantity of pure mercury* and then add weighed the sample tube in a vacuum. Because of rapid corrosion, samples containing gallium were of necessity prepared in a vacuum. To obtain the specific resistivity of an alloy the resistance of the sample containing the alloy was measured and compared with the resistance when the container was filled with mercury. Resistances were measured in the temperature range of 20" to 60°C to obtain the temperature coefficient of resistance. The electrical measurements were made by connecting the sample in series with the standard one-ohm resistance, and the potential drop measured alternately over the sample and the standard resistance. To correct for stray thermoelectric effects provision was made for reversing the direction of the current, and the true potential drop was taken to be the average of that obtained for the two directions of current flow. Various materials were used for the electrodes, the most uniform results being obtained with nickel. EXPERIMENTAL RESULTS The numerical results are presented graphically in Figs. 2 and 3 and in tabular form in Tables I and 11. Following are remarks on results of individual alloys. 1) Hg-In—This was the first alloy studied, and

Jan 1, 1960

By D. R. de Fontaine

By computing the values of the resolved shear stress for a great many orientations of the tensile axis on all 12 (111) <110> slip systems, Taylor and Elam&apos; were able to map out a stereogram of slip systems, given here, Fig. 1, in Diehl&apos;s notation (see, for example Hauser and Jackson&apos;). The purpose of the present note is to derive such a stereogram by mathematical reasoning and to give a simple method of defining the system with highest resolved shear stress for any direction of the tensile axis, thereby eliminating tedious computation of the Schmid factor. Let the tensile axis, of direction cosines [xyz], make the angles 0 and relative to the slip plane normal [HKL] and the slip direction [hkl] respectively. Fig. 2 shows a simple cubic cell whose edges define a Cartesian coordinate system. Let A be a unit vector of origin 0 supported by the tensile axis. Its end point [xyz] then lies on a sphere of unit radius, on the positive hemisphere of which the planes z = 0, x = y, y = z limit the so called primitive triangle of a standard [loo] stereographic projection. For any point of this triangle, the following hold: 0«2 «y *sx « 1 [l] Now, for given [xpz], the most highly stressed system will be the one for which the following expression of the Schmid factor has the largest possible value: (HKL) belonging to the form (111) and [hkl] to the form <110>, the denominator on the right hand side of Eq. [2] is equal to 1.fi.a. The unknowns H, ... h, . . . can now be determined by correctly distributing +1 and -1 to H, K, L, and +1, -1,O to h,k, 1 giving the numerator of Eq. [2] its greatest positive value (the angles 0 and cpare chosen acute) subject to the condition: Hh+Kk+Ll = 0 [3] since the slip direction must lie in the slip plane. Condition [3] can be satisfied only by having one of its terms vanish and the other two equal to +1 and -1. Taking the case of the tensile axis lying in the primitive triangle, x2y, z and therefore Hh will be chosen equal to +1 with H = h = +1 in order to retain a maximum of + signs. There remain two alternatives: either 1 = 0 or k = 0. 1) take 2 = 0 Then Kk = -1 and the numerator of [2] becomes: Retaining a maximum of + signs gives L = k = +1 and becomes: 2) take k = 0 Then L1 = -1and, likewise, the numerator of [2] becomes: xz - z2 + xy + yz [5] But the difference [5] - [4] can be written: (y - z)(x+y +z) [6] positive or zero by virtue of [I]. If [6] is positive (y > z), then the largest possible value for the numerator of [2] for any xyz inside the primitive triangle is given by [5], i.e., for: That is to say, the active slip system corresponding to an orientat:~on of the tensile axis inside the primitive triangle is:

Jan 1, 1962

By L. O. Brockway, W. C. Bigelow, J. A. Amy

Specimens of Inconel-X alloy solution-treated at 2050°F and aged for periods of 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F have been examined by electron microscopy and by electron and X-ray diffraction. Four minor phases were identified: titanium nitride, niobium nitride, an M23C6 complex carbide, and the intermetallic ? phase. The two nitrides were found in all of the aged specimens and in the solution-treated alloy, the y&apos; phase formed at all aging temperatures, while the M23C6 carbide formed only on aging at 1200° and 1400°F. Variations in the hardness, rupture strength, creep strength, and yield strength of the alloy have been shown to be related to variation in the size and distribution of the particles of the y&apos; phase within the matrix grains of the alloy, with maximum values of these properties occurring when there is a maximum amount of the phase present and a fine state of dispersion of the particles prevails. THE nickel-chromium alloys containing titanium and aluminum are widely used in applications requiring high strength at elevated temperatures. Studies on relatively simple ternary and quaternary alloys&apos;-4 have indicated that the favorable high-temperature properties of these alloys are related to the precipitation of an intermetallic ?&apos;-phase having a structure based On that of the Ni3A1 phase of the nickel-aluminum system. The present investigation was undertaken to identify the minor phases and to study the microstructural changes occurring in one of the more complex commercial alloys as a result of aging in the service temperature range, with particular emphasis on investigating the role of the ?&apos; -phase. The microstructural changes were studied by electron microscopy and the minor phases were identified by X-ray and electron diffraction. MATERIALS AND METHODS Inconel-X alloy was selected for this investigation because the previous studies of Frey, Freeman, and white6 provided extensive information on the variations in metallurgical properties of this alloy resulting from high-temperature aging treatments. Specimens aged 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F were made available for the present use. These were taken from 1-in. round-bar stock of a commercial heat having the following weight composition: 0.04 C, 0.56 Mn, 6.59 Fe, 0.007 S, 0.38 Si, 0.03 Cu, 73.22 Ni, 14.97 Cr, 0.78 Al, 2.38 Ti, and 1-02 Nb. They were solutjon-treated at 2050 for 4 hr and then water-quenched prior to aging. Powder X-ray diffraction patterns were obtained from insoluble minor phases which were separated from the alloys by digestion in the reagent of Mahla and Nielsen.6 Back-reflection patterns were obtained from electrolytically polished surfaces of the bulk search to detect the ?&apos;-phase&apos; Cu-K a radiation was used in both cases. In the electron-diffraction studies, the general method developed by Heidenreich, Sturkey, and

Jan 1, 1959

By George A. Roberts, Robert F. Mehl

When austenite first forms from aggregates of cementite and ferrite, it is not homogeneous.&apos; This inhomogeneity, consisting of both undissolved carbide and carbon concentration gradients, has a profound effect upon the characteristics of the austenite-pearlite reaction. The rate of formation of pearlite is increased by the presence of inhomogeneities2,3 and because of this (when the inhomogeneity is sufficiently pronounced) the hardenability of the steel is reduced.4,5 In addition to this kinetic effect, inhomogeneities will cause the direct formation of spheroidite from austenite at temperatures just below the Ael.6-11 The present report attempts quantitatively to evaluate the effect of inhomogeneity upon the rate of the austenite-pearlite reaction, presents a method of determining the austenitizing cycle necessary to obtain "practical homogenization," and considers the effect of inhomogeneity on hardenability. Effect of Inhomogeneities on Reactions Near Ae1 Few quantitative data are available representing the effect of undissolved carbide or of carbon concentration gradients upon the rate of the austenite-pearlite reaction. In procuring such data it is necessary to separate the effect of undissolved carbide from that of grain size, and this is not an easy task. The solution of carbide is always accompanied by an increase in the grain size, both effects contributing to the retardation of the reaction rate. It has been possible to make this separation and to obtain data that are independent of the grain size by the use of steels that differ only with respect to their tendency toward grain-coarsening. Steels C and D in Table I are such steels. These steels have been studied previously ;l,2,12 they differ only with respect to deoxidation practice; C was deoxidized with silicon while D, teemed from a portion of the same heat, was deoxidized with additional auantities of aluminum in the mold. C therefore is what is normally termed a "coarse-grained steel" and D is a, "fine-grained steel." These steels can be compared at the same grain size by heating c to a low temperature and heating D to an elevated temperature, producing a structure of austenite plus residual carbide in the former while forming homogeneous austenite in the latter; in such

Jan 1, 1943

By George A. Roberts, Robert F. Mehl

When austenite first forms from aggregates of cementite and ferrite, it is not homogeneous.&apos; This inhomogeneity, consisting of both undissolved carbide and carbon concentration gradients, has a profound effect upon the characteristics of the austenite-pearlite reaction. The rate of formation of pearlite is increased by the presence of inhomogeneities2,3 and because of this (when the inhomogeneity is sufficiently pronounced) the hardenability of the steel is reduced.4,5 In addition to this kinetic effect, inhomogeneities will cause the direct formation of spheroidite from austenite at temperatures just below the Ael.6-11 The present report attempts quantitatively to evaluate the effect of inhomogeneity upon the rate of the austenite-pearlite reaction, presents a method of determining the austenitizing cycle necessary to obtain "practical homogenization," and considers the effect of inhomogeneity on hardenability. Effect of Inhomogeneities on Reactions Near Ae1 Few quantitative data are available representing the effect of undissolved carbide or of carbon concentration gradients upon the rate of the austenite-pearlite reaction. In procuring such data it is necessary to separate the effect of undissolved carbide from that of grain size, and this is not an easy task. The solution of carbide is always accompanied by an increase in the grain size, both effects contributing to the retardation of the reaction rate. It has been possible to make this separation and to obtain data that are independent of the grain size by the use of steels that differ only with respect to their tendency toward grain-coarsening. Steels C and D in Table I are such steels. These steels have been studied previously ;l,2,12 they differ only with respect to deoxidation practice; C was deoxidized with silicon while D, teemed from a portion of the same heat, was deoxidized with additional auantities of aluminum in the mold. C therefore is what is normally termed a "coarse-grained steel" and D is a, "fine-grained steel." These steels can be compared at the same grain size by heating c to a low temperature and heating D to an elevated temperature, producing a structure of austenite plus residual carbide in the former while forming homogeneous austenite in the latter; in such

Jan 1, 1943

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.&apos; These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.&apos; These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By Carls Benedicks

It is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).l A study of the microstructure or local chemical composition of the metal (iron 70:30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the faot that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion&apos;72 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."3 In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corro~ion."~ On consulting the many textbooks on corrosion, as that

Jan 1, 1925

By Rufus J. Foster

During the discussion on the Preparation and Utilization of Sniall Sizes of Anthracite (page 613 of present volume), several inquiries were made concerning the use of the McClave grate, which was mentioned by Mr. Coxe as having proved satisfactory in the generation of steam at his collieries, and also at a large number of industrial estal)lishments in Scranton and elsewhere. For a more satisfactory repIy to such inquiries than could be furnished in the oral discussion, I have prepared the following paper to be included in the published proceedings. And, as the use of the fuel under consideration necessarily requires the employment of a blower to change the fire, from a condition giving an incandescent radiant heat only to one giving a hot gaseoua flame as well, I shall add a description of the McClave Argand blower and its method of action. The grate and blower combined form a complete and effective system fcr burning small fuels, such as anthracite culm, birdseye, buckwheat, bituminous slack, etc., in boiler and other furnaces; while the grate alone is now extensively used with the larger sizes of hard and soft coal in furnaces where blast is riot required. Fig. 1 is a view of the RlcClave grate as built in two sections. It is constructed on the principle best approved by practice to prevent warping and burning out; that is, it presents no long lines of

Jan 1, 1892

By Henry M. Howe

Henry M. Howe, Bedford Hills, N. Y. (communication to the Secretary.)*—Mr. Johnson&apos;s explanation, that the rounding of the graphite masses in oxygen-bearing cast iron is due to their being in part reprecipitated after re-solution in forming carbonic oxide temporarily with.that oxygen, is certainly most attractive and suggestive. It remains to be shown whether this rounding occurs also when the solidification is too rapid to permit this process to go on. J. E. Johnson might easily test this by casting a single ladleful of his oxygenated iron in masses of varying size. If this present hypothesis is true, then the rounding ought to increase progressively with the size of the casting, and with the distance from the outside, that is to say with the time available for re-solution and reprecipitation. I question whether a like benefit is to be expected even on this hypothesis, from the oxygenation of steel. The spheroidizing of graphite does good because graphite itself is so weak. But the constituent which can be spheroidized in steel is its cementite, which is a source of strength. Lamellar pearlite, in which this cementite in effect forms long den-drites, is far stronger than divorced pearlite, in which these dendrites have been broken up into spheroids. Even the surfaces of contact between ferrite and cementite are probably sources of strength because of the amorphous iron which probably fills them.

Jan 1, 1917

By H. O. Hofman

INSTITUTE OF TECHNOLOGY, In deternlining experimentally the fusibility of clays, two kinds of methods may be distinguished—the direct and the indirect. Of the direct methods, that of Seger has found

Jan 1, 1899

AlbioN S. Howe, San Francisco, Cal. (communication to the Secretary*):—In discussing this paper, &apos;I mould suggest that. the dip for iron pipe be liquid asphaltum, instead of coal-tar and pitch. Asphaltum is superior to coal-tar, and the variety

Jan 1, 1905

By Morris Muskat

A theory is presented for calculating the performance history of complete water-drive systems producing from idealized stratified formations. The general equations are applied to systems where the permeability stratification is either of the exponential or linear type. Calculations were carried through for different degrees of permeability stratification, but with special emphasis on the effect of the mobility ratio between the produced oil and the invading water on the resultant performance. These results are also expressed graphically as curves for the initial water breakthrough recovery, for the different degrees of stratification, as a function of the mobility ratio, and of the composition of the produced fluid stream as a function of the cumulative oil recovery. For several typical cases the latter has also been plotted as a function of the cumulative oil and water throughflow. The general result is that when the mobility of the oil is lower than that of the invading water the channelling tendency resulting from the permeability stratification becomes aggravated as the higher permeability zones become flooded out. Situations of this type would obtain when producing low gravity or highly viscous oils. Conversely, if the mobility of the oil is high compared to that of the invading water, the flooding of the high permeability zones will lead to a retarding and choking effect, and the gross bypassing phenomena will be partially suppressed. These conditions would correspond to those of flooding high gravity or low viscosity oils. A discussion is given of the various basic assumptions made in the analysis, including that of ignoring the stripping phase of the production history as implied by relative permeability concepts. INTRODUCTION The physical ultimate recoveries from oil reservoirs are basically determined and limited by the physical oil displacement processes associated with the reservoir producing mechanism. In practice, however, the economic ultimate recoveries are further limited by the mobility of the reservoir fluids and the uniformity and continuity of the producing formation. In fact, it is the differential depletion between the component parts of the composite reservoir which ultimately determines the total recovery at the time of field abandonment. While this observation applies to both the solution gas drive and gravity drainage mechanisms, in which use is made only of the energy contained within the original oil-bearing reservoir, it is of even more paramount importance under operations wherein the energy associated with extraneous fluids provides the ultimate oil expulsion mechanism. Whether the invading fluid is the water from an edgewater drive, water injected for pressure maintenance, gas injected for pressure maintenance, or gas returned to the formation in a cycling program, it is often the continuity and uniformity of the producing section which will control the economic efficiency of the operations. The importance of the problem of reservoir non-uniformity does not, of course, lessen its complexity or the difficulties of its solution. In fact, these are inherently such that the concept of a "general" solution is virtually meaningless. About all that can be reasonably hoped for is the analysis of specific and well-defined types of non-uniformity which may give some degree of approximation to actual reservoir conditions. Since variations in the nature of the reservoir which depend only on the position along the streamlines will not lead directly to major differential depletion development within the reservoir, the types of non-uniformity considered thus far have involved stratification assumptions. That is, the producing section has been replaced by a multi-layer "sandwich," each uniform areally, and differing from the others only in its basic physical constants as to thickness, porosity and permeability. The fluid motion in the composite system is thus approximated by a parallel superposition of the independent fluid movements in the individual strata. For the specific application to cycling operations the theory of the effect of permeability stratification has been developed for both discontinuous&apos; and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear&apos; or probability3 functions. In all these studies complete dynamical equivalence was assumed between the injected dry gas and the displaced wet gas. The overall effective permeability of each stratum was therefore considered as constant and independent of the degree of invasion of the injected fluid. In the case of the displacement of oil by water, the assumption of dynamical equivalence between the water and oil will be strictly valid only by accident. Even if the oil viscosity should be the same as that of the water, the effective permeability to the oil in the presence of the connate water will in general be quite different from that of the water behind the water-oil interface flowing past the trapped residual oil. As a result the effective permeability for the stratum as a whole and rate of water invasion will change with time as the intrusion continues. The differential fluid motion in the individual strata will thus also vary with time. Qualitatively, it is easy to predict the resultant effects. If the permeability to viscosity ratio of the invading fluid exceeds that of the fluid displaced, the stratification and bypassing effect of the perme-

Jan 1, 1950

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow&apos; and frontal advance&apos; equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas&apos; reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water &apos;front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By Charles H. White

Methods in colorimetry are based on the assumption that the intensity of the&apos; color of a definite volume .of solution is directly proportional to the quantity of the color-producing substance present. In the preparation and examination of colored solutions there are three ways in which the depth of color may be varied. These variables are : (1) the quantity of&apos; the coloring matter; (2) the quantity of the solvent, or the dilution ; and (3) the thickness or depth of that portion of the solution examined. With these three variables as a basis, three general methods in colorimetry have been devised, all of which have been used in the determination of carbon in steel. In the first method, the quantity of the solution is kept the same for both the unknown steel and the standard, and the sections compared are of equal thickness, while the quantity of the standard is varied until the color obtained is of the same intensity as that produced by a definite quantity of the unknown steel. In laboratories where this method is used there is prepared and kept for permanent use a series of solutions with varying amounts of the standard, representing the percentages of carbon from the lowest to the highest demanded in that laboratory. These standard solutions are kept in bottles or test-tubes of equal diameter, and are arranged in series from the faintest to the most intense color, so that it is a simple matter to find the place of the unknown steel in the series, when the solution is of a definite volume and is contained in a tube of the same diameter as the standard tubes. In the second method, equal quantities of the standard and of the unknown steel are dissolved, the standard is diluted to a definite volume, and the solution of the unknown steel is di-

Jan 1, 1907

By Alexander Bowie

In many places throughout the Western mountain plateau regions of the United States coal beds in place have been burned over very extensive areas, the fire evidently originating on the nakedly exposed outcrop of the coal bed and gradually burning its way into the bed for considerable distances under very heavy cover. The surface evidences of the burned-out coal beds are seen in the calcined and discolored rocks overlying the places of the outcrops. The greater the mass of the burned coal the higher the results of its combustion can be seen in the overlying strata. I have noted many instances of this condition in the States of South Dakota, Wyoming, Colorado, New Mexipo, and Arizona. In the lignite fields of Dakota and Wyoming I noted stretches of level country many square miles in extent where the surface rooks were roasted and vitrified by the burning of a great bed of lignite lying nearly level and with a light cover; this is probably the most favorable natural condition for the burning out of a coal bed. The less the depth of the rock covering overlying the coal bed, the better the chance for a continuous supply of air to the fire; but when the coal bed dips heavily into the ground, or even if level, if it passes under a hill or mountain which gives the bed a heavy covering of strata, the fire has more chances of being extinguished from natural causes than in the first condition described. The distance which a crop fire may extend into a coal field is very much influenced by the dip, the thickness of the coal bed, and the nature of the rock covering immediately overlying it. In reasoning on this subject, it would seem logical to assume in the case of a coal-bed cropping at the base of a hill and dipping into it, with an extensive drainage surface above the crop line, that a crop fire would be promptly extinguished by the caving in of the overlying strata and the precipitation of the rainfall from the drainage surface above the outcrop through the breaks formed in the caving strata. This consideration would be more or less effective according to the climate of the location and the nature of the overlying strata. In a humid climate where the rainfall was heavy the water from the natural precipitation alone would probably extinguish a crop fire before it could work its way very far under cover, but in an arid climate this preventive does not seem to be effective.

Jan 1, 1915

By G. E. Anderson

THE Asientos-Tepezala district is in the north of the State of Aguascalientes, about 30 miles north of the city of Aguascalientes, the capital. The district is reached by a standard-gage railway on the west side through the junction, Rincon de Romos, which is on the main line of the National Railways of Mexico from El Paso to Aguascalientes. The terminal is Tepezala. On the east side a narrow gage connects Asientos with the junction, San Gil, on the main line, Asientos to San Luis Potosi. Tepezala on the west side of the Asientos hills is about 2 miles from Asientos on the east side. The area between the two mining centers is separated by a low subued divide which forms the central part of the hills. The district is in a group of isolated hills surrounded by characteristic bolson plains. The hills rise above the surrounding plains about 6500 to 10,000 ft.; the highest peak is Alta Mira. The two mining districts lie somewhat upon the flanks of the hills at about the same elevation, 7200 ft. The district is an old one and has been known since early in the 17th Century when the mines were worked by the Franciscan Monks. Their mining operations which were limited to the oxidized ore above the water level, consisted chiefly in extracting silver from the Santa Francisca vein. To judge from the old workings and the remains of surface plant, the operations were on a large scale. By modern mining operations since about 1900, the various mines of the district have been one of the principal sources of ore for the smelter located at Aguascalientes.

Jan 2, 1926

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By Juan Sodi, John F. Elliott

The standard free energy of ReS2 has been measured in the range of 1050° to 1250°K using H2/H2S mixtures and a slight variation of the method described by Hager and Elliott.1 The result is: The experimental method and apparatus were modified slightly for this study. Measurements on Cu2S were made to verify the application of the method to the work on ReS2. THE EXPERIMENTS AND RESULTS Briefly, the experimental method consisted of exposing a chip of copper or rhenium at a known temperature for 8 hr to a slowly flowing gas stream at the same temperature in which Ph2S and PH2 were known. The chip was withdrawn quickly from the hot furnace, and subsequently it was inspected for the presence of a sulfided surface. In the experiments described here, there was no ambiguity in any case as to the presence or the absence of the sulfide. At a given temperature, gas compositions for sulfidization were explored systematically until two compositions were found whose values of ?G°, Eqs. [I] and [2], were within approximately 100 cal of each other, one of which was sulfi-dizing and the other was not. These are termed the "straddle" compositions and it is assumed that the equilibrium composition lies between them. The chief modification to the apparatus, which is shown schematically in Fig. 1 of Ref. 1, was to support the metal specimen on a small alumina boat which could be moved along the reaction tube, 6 mm ID, by platinum wires. An appropriate seal at each end of the reaction tube permitted the sample to be moved from the cold end of the tube into the hot zone in 2 to 3 sec, and the sample could be withdrawn equally rapidly. Thus, it was possible essentially to quench the specimen from the reaction temperature with the reaction gas or helium flowing and without danger of breaking the reaction tube. The usual practice at the end of the experiment was to switch the gas system to the helium tank, flood the reaction chamber with helium, and pull the sample out of the hot zone. The purpose of the modification was to permit study of the sulfidization of copper without the complication of the back-reaction between the gas and the specimen as the latter cooled during slow withdrawal of it from the hot zone; this was a problem in the earlier work.&apos; A further improvement located the tip of the temperature-indieating thermocouple and the specimen precisely at the hottest part of the furnace. A carefully calibrated thermocouple, with its tip at the position of the specimen and with other conditions duplicating those of an actual experiment, showed that in the temperature range of 900° to 1122°C the temperature of the specimen differed from that of the tip of the indicating thermocouple by less than 0.5°C. The two positions were 0.5 cm apart. The reaction gas was prepared from ultrahigh-purity hydrogen (<l ppm O2, <0.5 ppm H2O) and CP grade hydrogen sulfide (99.5 pct H2S). High-purity helium (99.995 pct He) was used. All of these gases were purchased from the Matheson Co. All flow meters were recalibrated by the soap-bubble method with hydrogen, H2S, helium, and several gas compositions used during the study. These calibrations gave a linear relationship with a slope of 1.0 for the plot of log flow rate vs log pressure drop across the flow meter, in accordance with the Hagen-Poiseuille equation. The analysis of the gas was determined in the same manner as was reported previously. Good checks were obtained between the composition of the gas established by the flow-meter settings and by chemical analysis of the gas taken after the mixing bulb and ahead of the furnace. The pressures of H2S, H2, S2, and HS in the equilibrium gas at temperature were calculated from the following data :3 The pressures of the species S and S8 were negligible for the conditions of the experiments.3 There was no sign of vaporization of ReS2 either by weight loss or deposits in the reaction tube. Thus it is not possible to account for the apparent volatility of the compound reported by Juza and Biltz.2 The inlet gas composition and the calculated equilibrium ratio of PH2 S/PH2 for the "straddle" points of each experiment are shown in Table I. The specimens of metal for the experiment were small clippings of annealed copper (99.9+ pct) sheet 0.005 in. thick that was obtained from Baker and Adamson and of "high-purity" rhenium (99.9+ pct) sheet 0.005 in. thick that was purchased from Chase Brass and Copper Co. A specimen was removed from the apparatus; inspected for the presence of the sulfide, and then stored in a sealed vial. A fresh clipping was used in each measurement. The condition of the surface of each specimen after the experiment is noted in Table I.

Jan 1, 1969