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By Zay Jeffries

The object of the present paper is to enlarge somewhat on the general principles advanced in my discussion1 of Mathewson and Phillips' article on The Recrystallization of Cold-Worked Alpha Brass on Anneal-- ing.2 It will also serve as an acknowledgment of Prof. Howe's most important remarks on my contribution. In this paper the writer has adopted Prof. Howe's suggestion to substitute the term "germinative temperature'' for "critical temperature for grain growth." Instead of being an exact or certain temperature it should be considered that the germinative temperature phenomenon exists throughout a small temperature range. v Factors Influencing Fast Growth Phenomena The development of grains of macroscopic size at the germinative temperature should be considered the extreme condition of a general rule. When considered in this light it is not strange that the development of these large grains should be the exception and not the rule. The principal factors influencing the operation of the laws of fast growth temperature are as follows: . 1. Rate of heating. In the original paper,' the germinative temperature was defined as "the minimum temperature at which two adjacent grains can coalesce to form one larger grain, provided that this larger grain will have sufficiently increased its power of attack, to enable it to absorb adjacent grains which cannot coalesce with each other. Time is always to be understood as a factor governing the first stage of grain growth." If the time of heating is short, the germinative temperature is raised. The formation of large grains in metals may occur at relatively high temperatures when the rate of heating is rapid. It is to be understood that in such cases, grain growth

Jan 1, 1917

By Tormod Forland

FROM equilibrium measurements on the system NaF-Na 3A l Fo-A 1 2 O 3-Na CO 3-CO 2 with high contents of NaF, Forland, Storegraven, and Urnesl concluded that complexes are formed containing two oxygen, three aluminum, and a less defined number of fluorine per complex. The same number of oxygen atoms per complex was also found by cryoscopic measurements for mixtures high in NaALF 6. In a recent paper by Stokes: some other complex ions, Al2O2F42- and AlOF2-, have been suggested. Here an additional argument in favor of the complex ALO2F. suggested by Forland, Storegraven, and Urnes will be given. When fused Na3AlF6 containing some A12O3, is cooled slowly, the solid phase will consist of the two components as separate phases. The melting point and the heat of fusion of Al2O3 are so high that this component will form the stable solid phase even though in the liquid state the complex may have a high stability. If, however, the fused mixture is quenched, the decomposition of the oxygen-containing complex and the formation of solid Al2O3 does not proceed fast enough, and a solid solution of A12O3 in Na3AlF6 is obtained. Zintel and Morawietz3 obtained cryolite containing 10 pct AL2O3 in this way. The density and the lattice parameters of the A12O3 containing cryolite were also measured, and from this it was concluded that the Al2O3 enters the cryolite lattice as Al3AlO0 groups replacing Na3AlF6 groups. However, the experimental data could as well be explained by assuming that one Na+ ion and two of its neighboring F- ions are replaced by one Al3+ ion and two O2- ions. This may be pictured schematically as: F F F F F F F Al F Na F Al F ,-Na+ + Al8+ F Al 0 A1 0 A1 F F F F —2 F- + 2O2- F F F solid cryolite cryolite-alumina solid solution This means that the complex in the solid solution, derived from X-ray and density measurements, is the same as that which Forland, Storegraven, and Urnes derived from equilibrium measurements in the liquid state. References IT. Forland, H. Storegraven, and S. Urnes: Ztsch. fur anorgan-ische und allgemeine Chemie, 1955, vol. 279, p. 205. 2J. J. Stokes: AIME Trans. To be pubhshed. s E. Zintel and W. Morawietz: Ztsch. pubhshed.fur anorganische und allgemeine Chemie, 1939, vol. 240, p. 145.

Jan 1, 1958

By N. B. Aughenbaugh, W. C. Patrick

The availability of a thorough, simple-to-use roof fall classification system is desirable for several reasons. First, such a system would expedite the reporting of falls for the purposes of estimating material removal costs, analyzing damage levels, and complying with federal regulations to report falls in certain areas of the mine. Second, the classification system would allow the mining engineer to record falls routinely with little time and effort expended. This would encourage him to make observations concerning what type of roof support would work best in a given situation. Third, and probably most important, an

Jan 1, 1980

By N. B. Aughenbaugh, W. C. Patrick

The availability of a thorough, simple-to-use roof fall classification system is desirable for several reasons. First, such a system would expedite the reporting of falls for the purposes of estimating material removal costs, analyzing damage levels, and complying with federal regulations to report falls in certain areas of the mine. Second, the classification system would allow the mining engineer to record falls routinely with little time and effort expended. This would encourage him to make observations concerning what type of roof support would work best in a given situation. Third, and probably most important, an

Jan 3, 1979

By J. Lohrenz, C. R. Clark, B. G. Bray

Procedures to calculate the viscosities of in situ reservoir gases and liquids from their composition have been developed and evaluated. Given a composition expressed in methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide together with the molecular weight and specific gravity of the heptanes-plus fraction, the procedures are capable of calculating the viscosity of the gas or liquid at the desired temperature and pressure. The procedure for reservoir liquids was developed using the residual viscosity concept and the theory of corresponding states, and was evaluated by comparing experimental and calculated results for 260 different reservoir oils ranging from black to highly volatile. The average absolute deviation was 16 per cent. This is the first known procedure for calculating the viscosity of reservoir liquids from their compositions as normally available, i.e., including the heptanes-plus fraction. The procedure for reservoir gases uses a sequence of previously published correlations. Evaluation of the procedure was accomplished by comparison of 300 calculated and experimental viscosities for high-pressure gar mixtures in the literature. The average absolute deviation was 4 per cent. The calculations are useful for (I) determining viscosities in compositional material balance computations and (2) predicting the viscosity decrease which occurs when gases, LPG, or carbon dioxide dissolve in reservoir oils. INTRODUCTION Methods to predict viscosities of reservoir fluids from the normally available field-measured variables have been presented. Beal,1 Standing,2 and Chew and Connally3 orrelated oil viscosities with temperature, pressure, oil gravity and gas-oil ratio. Carr, Kobayashi, and Burrows4 and Katz et al.5 have presented correlations for reservoir gas viscosities as a function of temperature, pressure and gas gravity. Lie all intensive physical properties, viscosity is completely described by the following function: Eq. 1 simply states that viscosity is a function of pressure, temperature and composition. These previous correlations1- hay be viewed as modifications of Eq. 1, wherein one assumes more simple functions may be used. The assumptions are practical, because the composition is frequently not known. Further, the assumptions are sufficiently valid so that these correlations are frequently used for reservoir engineering computations. In compositional material balance"' computations, the compositions of the reservoir gases and oils are known. The calculation of the viscosities of these fluids using this composition information is required for a true and complete compositional material balance. For reservoir gases, Carr, Kobayashi and Burrows4 have presented a suitable compositional correlation. For reservoir oils, no correlation is available, and data from reservoir fluid analyses have been used7-9 for compositional material balance calculations.* From a theoretical point of view, this is entirely invalid. The reservoir fluid analysis, whether flash, differential, or other process, does not duplicate the compositions which occur during the actual reservoir depletion process, therefore the viscosities measured during reservoir fluid analysis are not those which occur in the reservoir. From a practical point of view, the "error" of using viscosities from reservoir fluid analysis is of varying and unknown significance. One can say qualitatively that the error is greatest where compositional effects are greatest, i.e., for volatile oil and gas condensate reservoirs and pressure maintenance operations. The first requirement to obtain a quantitative estimate of the significance of the error is to develop a reliable compositional correlation for the viscmities of reservoir oils. No such correlation has been available. Consistent with this requirement, the objective of this study was to develop a procedure to predict the viscosity of reservoir fluids from their compositions. Normally, the compositions of reservoir fluids are available expressed as mole fractions of hydrogen sulfide, nitrogen, carbon dioxide and the hydrocarbons methane through the heptane-plus fraction, with the average molecular weight and specific gravity of the latter. The final correlation was to use the composition in this form. While the more challenging objective of the study was the development of a correlation for the viscosities of reservoir oils, the viscosities of reservoir gases were also studied. The end result of the study was a procedure to calculate the viscosities of reservoir gases and liquids suitable

Jan 1, 1965

By S. F. Shaw

THE principles involved in lifting oil in wells flowing naturally are identical with those underlying the flowing of wells by means of the air-gas lift, and information of a dependable nature obtained in the study of the air-lift can be applied to wells with natural flow. A well flowing naturally is one in which the lifting is done by means of the gas-lift, for which the gas is supplied entirely by the formation from which the oil is derived. In air-gas lift operations, there is insufficient gas supplied by the formation to lift the oil to the surface in an efficient manner, therefore additional gas for this purpose must be furnished from an outside source. There may, at times, be conditions obtaining in natural flowing wells different from those in wells flowed by gas-lift, but these differences do not at all conflict with the main principles of gas-lift work. One such condition is met with in wells in which the gas supplied by the formation is in considerable excess of that required to lift the oil to surface; this excess may be so great as to reduce the quantity of oil that can be lifted through the particular diameter of casing or tubing that has been lowered into the well. This same condition can be brought about, however, by supplying a large excess of gas from an outside source to an artificial gas-lift well, and a study of the effects obtained from injecting a large excess into the well can be applied directly to handling wells flowing naturally which have a large excess of gas supplied by the underground reservoir.

Jan 1, 1929

By T. A. Dungan

The thermal processes for the production of metallic magnesium can be divided into two general classifications, the direct reduction of magnesia with carbon and the indirect reduction of compounds of magnesium by reducing agents that are themselves products of carbon reduction. The latter are so chosen as to cause reduction of magnesium compounds wherein only the magnesium is liberated in the vapor phase. Reducing agents used are: calcium carbide, silicon carbide, silicon, aluminum, various silicides or combinations of calcium, aluminum, silicon in iron. All of these are products of highly endothermic reactions and, with the exception of scrap aluminum, can be produced in an open, submerged arc furnace; that is, the arc is covered only by the charge itself. The more investment in energy required to prepare such a reducing agent, the less is the energy required in the subsequent step to reduce the magnesium compound to the metal. It is impossible, however, to avoid the laws of thermodynamics, no matter how much circumambulation is resorted to in the preparation of successively more powerful reducing agents. Since each such step carries forward its own inefficiencies, it appears evident that the ultimate status of such processes is dependent upon the development of by-products. The direct reduction of magnesium oxide by carbon has a decided appeal to both the scientist and the industrialist. The successful production of the carbo-thermic plant at Permanente is a significant fact in the substantiation of this concept. Like most developments, however, the history of carbon reduction of magnesia is not one of triumph after triumph, or immediate heady success to the investigators. It is understood that one of the early investigators conducted an experiment wherein he placed carbon and magnesia in one end of an evacuated tube and managed to heat this end to a temperature high enough that magnesia and carbon deposited at the other end of the tube. The charge, unreduced, appeared to have been completely transported from the hot to the cold end of the tube. This raised doubt for some time as to whether magnesia could be reduced at all with carbon. It was correctly suspected, however, that the magnesia was in fact reduced and the resultant magnesium vapor and carbon monoxide reacted upon one another upon reduction in temperature to reform the starting ingredients. Attempts were then made to dilute the two vapors by passing a considerable stream of hydrogen through an arc furnace charged with magnesia and carbon. Thus by dilution of the products it was' expected to obtain metallic magnesium. The results were positive and metallic magnesium was .0

Jan 1, 1944

By Edmund Kirby

THE results to come from the application of cheap oxygen to industry in general will be so great that it is not possible to enumerate them beforehand and still less to estimate them. We naturally think first of the fuel to be saved; yet this is only a minor item. The main results will be changes in methods of manufacture or of operation. The speed of operation will be greatly increased, with consequent savings in labor and fixed charges, and also, in most cases, in the cost of fuel. High temperature will be brought within the reach of every manufacturer, whereas it is now available only to those operating expensive electric furnaces located within reach of large water power. New speeds and new temperatures mean improvements and processes not thought of at present. Incidentally the changes in methods will probably change the location of important world industries, the tendency being to concentrate at the fuel centers. The whole subject is so new that most of the data which an engineer requires for definite estimates do not exist. All that is possible now is to obtain a general view of the subject with rough and fragmentary estimates for some of the industries with which we are specially concerned. Most of the figures presented deal with fuel saving merely because there are available no data from which to estimate the effect on speed of operation. When working out the practical problems involved in substituting oxygen for air, in most cases the change will be made step by step; by trying out air enriched with increasing percentages of oxygen. Such partial applications of oxygen will be temporary expedients during the transition and there will be no stopping place short of the complete substitution of air by oxygen. This final stage is therefore the one discussed in this paper.1

Jan 11, 1924

Edward Keller, Baltimore, Md. (communication to the Secretary): When, at the New Pork meeting, February, 1899, Mr. Douglas gave an abstract of his highly interesting paper on the Copper Queen mine, he invited the members of the Institute, in his usual progressive spirit, to make a full scientific investigation of the region of that mine during the prospective excursion to Bisbee, Arizona. I volunteered to examine some of the metallurgical processes and products of the works, and obtained from Mr. Douglas a valuable series of samples. Upon the issue of his paper, however, I found that he had already a considerable volume of analyses of those products, and that little was left for me to do in that respect, except to duplicate his results, the importance of which work would not have been commensurate to the time and labor involved. I selected, therefore, only some points which he had not made entirely clear, or concerning which I was skeptical. The details of most of my work will appear in a future paper. From Mr. Douglas's figures I have calculated the values for the elimination of impurities in the so-called Leghorn converter, introduced by him at the Copper Queen works, and have found them to be as follows: Percentage of Elimination of Impurities in Pour Blows of a Converter. No of ' Selenium Sulph'r Iron. Zinc. I Nickel. Lead. Antimony Arsenic. and Blow- ! Tellurium .. 1.......... 99.4 99.6 88.0 92.6 94.4 81.6 83.8 40.3 2.......... 99.0 99.6 98.1 92.5 96.8 71.9 76.6 38.1 3.......... 98.8 99.5 93.5 91.4 96.3 63.8 80.6 25.3 4.......... 99.8 99.5 95.8 95.8 97.5 65.3 76.9 36.3 Average 99.2 99.6 93.8 93.1 . 96.2 70.6 ! 79.5 35.0

Jan 1, 1900

By B. E. Eakin, R. T. Ellington

An apparatus and a procedure for determining the viscosity behavior of hydrocarbons at pressures up to 10,000 psia and temperatures between 77 and 400° F are described. The equipment is suitable for measuring viscosity of either the liquid or vapor phases or the fluid above the two-phase envelope for systems exhihiting retrograde phenomena, according no the phase state of the system within these ranges of temperature and pressure. Equations are developed for calculation of viscosity from the experimental measurements, and new data for the viscosities of ethane and propane at 77° F are reported. INTRODUCTION With the advent of higher pressures and temperatures in industrial processes and deep petroleum and natural gas reservoirs, demand has increased for accurate values of physical properties of hydrocarbons under these conditions. Proportionately, more frequent occurrence of natural gas and condensate-type fluids is encountered as fluid hydrocarbons are discovered at greater depths. This increases the importance, to the reservoir engineer, of being able to predict accurately the physical properties of light hydrocarbon systems in the dense-gas and light-liquid phase states. Reliable gas viscosity data are limited primarily to measurements made on pure components near ambient temperature and at low pressures. Few investigations have been reported for high pressures, and except for methane, data on light hydrocarbons are subject to question. This is demonstrated by the large discrepancy between sets of data on the same component reported by different investigators. For mixtures in the dense gas and light liquid regions and for fluids exhibiting retrograde behavior there are very few published experimental data. Viscosity data for methane have been reported by Bicher and Katz,1 Sage and Lacey,12 Comings, et al,3 Golubev,3 and Carr,3 with good agreement among the last three sets of data. Comings, Golubev and Carr utilized capillary tube instruments for which the theory of fluid flow is well established. The theory permits calculation of the viscosity directly from the experi- mental data and dimensions of the instrument alone. Sage and Lacey, and Bicher and Katz used rolling-ball viscometers. The theory of the rolling-ball viscometer has not been completely established, and these instruments presently require calibration by use of fluids of known viscosity behavior before viscosities of test fluids can be measured. To obtain accurate data it is necessary that the rolling-ball viscometers be calibrated by use of fluids of density and viscosity similar to the test fluids, a difficult selection for the gas phase. From the methane data and experimental tests on various natural gases, Carr developed a correlation for predicting the PVT behavior of light natural gases.2,3,4 This correlation was based on data for a very limited composition range; its application to rich gases and condensate fluids is questionable. The object of this investigation is to develop an instrument which can be used to obtain viscosity data at reservoir temperatures and pressures, for rich gases, condensate-type systems above the two-phase envelope and light liquid mixtures. These data will be used in an effort to develop correlations to represent the viscosity behavior of these fluids. APPARATUS In a previous viscosity study Carr2 utilized a modified Rankine capillary viscometer configuration," Fig. 1. In this instrument the gas to be tested is forced through the capillary tube in laminar flow by motion of a mercury pellet in the fall tube, the measured displacement time being that required for the mercury slug to move between the brass timer rings. The viscometer is constructed of glass and mounted in a steel pressure vessel. The test gas pressure in the viscometer is balanced by an inert gas (usually nitrogen) in the vessel. Excellent results have been obtained with instruments of this type, with Carr2 and Comings5 reporting repro-ducibilities of 99.5 to 99.3 per cent and an estimated absolute accuracy of 99 per cent. However, these instruments have limitations which have precluded their use for liquids. The need for maintaining a balance between pressures of the test fluid and inert gas in the viscometer vessel presents operating problems, and requires charging the test fluid to the viscometer very slowly. The principle drawback to the Rankine unit is behavior of the mercury slug which provides the pressure differential across the capillary. When even trace quantities of propane or heavier hydrocarbons are present in the test gas, the mercury tends to subdivide

By W. C. Roberts-Austin

The subject with which the Council of the American Institute of Mining Engineers has entrusted me is one of much interest. It has been so admirably treated in America by Prof. Carl Barus* that I should have hesitated to deal with it had not the adoption of pyrometric methods in England recently occupied much attention, especially in relation to metallurgical industries and research. I shall endeavor to show what is the present state of our knowledge of practical pyrometry by briefly tracing the history of the efforts which have been made to measure high temperatures. This paper will, therefore, be limited to the consideration of those forms of appliance which have either marked distinct stages of advance, or have remained in use with more or less modification through a considerable range of time. The earliest pyrometers were essentially thermoscopes, and although their graduation presented great difficulties, their importance as affording a means for the measurement of high temperatures has been recognized for centuries. It would be difficult to illustrate this better than by a brief record of the testimony which has from time to time been offered by those who have had to apply the heat of furnaces in research or in industry, and it is mainly for the sake of the light incidentally thrown on the progress of both that the following historical notes are offered. In the eighth century, Geber, the chemist, wrote a treatise on furnaces, and showed that he was familiar with many and varied means of applying heat; but he points to the difficulties that are met with in conducting operations at high temperatures, which he attributed to inability to measure heat, his actual words being: " sed quoniam non est res ignis, quae mensuari possit." t

Jan 1, 1894

By Edwin C. Holden

In making the original estimates for a report recommending the cyanidation of Ymir stamp-mill tailings, the writer was unable to find in any of the standard works on cyanide-practice certain data applicable to the local conditions; nor has he as yet seen quite the same practice recorded in the rapidly growing literature of cyanidation. To present these figures, together with a few novel features of local practice, the present paper is offered. The ore treated is obtained from a fissure-vein of steep dip, occurring in a slate country. The ore-body is lenticular in plan, swelling from 4 ft. in width at one end to a maximum of 42 ft., and tapering irregularly to less than 18 in., where payvalues cease. In the wider portions of the fissure the ore is mixed with more or less horse-matter from the walls. The clean ore is white, massive quartz, with from 8 to 12 per cent of sulphurets; the latter being pyrite, sphalerite and galena, the predominance being in the order given. The precious metal tenor is variable, the gold more closely following the pyrite, the silver the galena. The present mill-supply is practically all from below the oxidized zone. The unavoidable admixture of horse-matter and stope-filling with the ore as mined, affects more or less the character of the mill-feed, which sometimes contains from 10 to 25 per cent of slate. During the last three months of 1902, the mill-feed carried 0.3977 oz. gold and 1.903 oz. silver per ton of 2,000 lb., 2.65 per cent lead and 2.92 per cent zinc. The iron, unfortunately, was not determined. The Ymir mill and mine have been fully described elsewhere;* suffice it to say of the milling that the crushed ore,

Jan 1, 1904

By A. H. Daane, J. F. Haefling

BECAUSE of the wide use of platinum in industry and research, the physical properties of this metal, including its vapor pressure, have been studied in some detail.' The other members of the palladium-platinum group of metals have not been studied as extensively, and only qualitative information is available on the vapor pressure of palladium. Data given in literature by Vines1 and Brewer2 on the vapor pressure of palladium are based on the qualitative observations by Holborn and Austin3 and Crookes4 on the rate of volatilization of palladium filaments in various atmospheres. The general observation that palladium is the most volatile metal of the palladium-platinum metal group was corroborated by Bell, Love and Normand who studied the separation of isotopes of the platinum-group metals by a mass spectrometric method. We have measured the vapor pressure of palladium using the Knudsen effusion technique. In this work, the effusion vessel was suspended from a quartz-fiber microbalance into an induction furnace, and the amount of vapor effusing from the vessel was determined by direct weighing of the vessel during the measured heating times. This technique has been described in a report from this laboratory." The vapor pressure of palladium was calculated from these measurements using the equation P...... = 17.14 -W- (77m)'u [1] a t where ? is the weight loss in grams of vapor of molecular weight m from a vessel having an orifice of a sq cm, during t sec. The derivation of this equation from kinetic theory has been described in a previous report from this laboratory: as well as in texts discussing the kinetic theory of gases.%" Test Vessel—In the search for a suitable material for the effusion vessel, it was found that tantalum reacted with palladium metal to form intermetallic compounds, and graphite was readily dissolved in palladium metal to form what appeared to be a liquid phase at a temperature several hundred degrees below the melting point of palladium. On cooling, the graphite gathered into spherical balls in the palladium, with crystals extending radially from the center of these balls, some of which were a millimeter or more in diameter. However, palladium metal vapor did not attack the graphite vessel, so graphite could be used where it did not contact condensed palladium. Tungsten did not appear to react with palladium vapor or molten palladium at its melting point, but it was not convenient to use a tungsten-vapor pressure vessel because of the difficulty of fabricating this metal. Since the vapor-pressure range to be studied (10 2 to 10 ' mm) did not appear to extend above the melting point of palladium, a combination of tungsten and graphite served to provide a very satisfactory effusion vessel. The lower half of the graphite vessel was lined with some strips of tungsten foil and the sample of palladium consisting of a coil of sheet was placed in the tungsten liner; in this way, no contamination of the palladium by carbon occurred. Procedure After outgassing at 1500C, the tungsten-lined graphite effusion vessel was loaded with 300 mg of

Jan 1, 1959

By R. Wiesenthal

A method is developed for improving the low recovery efficiency which results when viscous oils are flooded by water. Viscous oil has been diluted with a lighter liquid miscible in it in any ratio which produces a mixture possessing a reduced viscosity and which is then displaced by water. Light gasoline was used in these tests to reduce the viscosity of the oil in place. Oils possessing viscosities in the range of 1.28 to 324 cp at the test temperature of 30C were displaced from a cylindrical unconsolidated sand core, with a length of 2 m (6.6 ft) and a diameter of 10 cm (3.9 in.) at a flood of 6.27 cc/sq cm/hr. In two test series up to I PV of light gasoline was injected into the core before water flooding. In the first series the recovery of a low-viscosity oil (1.28 cp) increased as the volume of light gasoline was increased. However, only the oil which could not be recovered by water flooding alone could be replaced by the light gasoline. In the other series, the recovery of a more viscous oil (13.5 cp) was not increased even if large quantities of light gasoline were injected. An oil bank built up ahead of the water front so that the flood water met with equivalent saturation conditions, as would be the case in flooding solely with water. However, the recovery of more viscous oils could be increased substantially when the core was first flooded with water, followed by a slug of light gasoline, and then flooded with water again. Furthermore, an oil bank ,built up ahead of the second water front. The formation of this oil bank is particularly favorable for the displacement process; the greater part of the light gasoline injected was pushed out of the core ahead of the oil and recovered. Using a light oil of low viscosity, it was possible to replace only the residual oil that could not be recovered by water flooding by the light gasoline. As the basic study had shown that highly viscous oils could be recovered by flooding first with water, then with light gasoline, followed by a second injection of water, the study was extended by tests made with reservoir fluids and cores taken from the low-gravity oil reservoir of the Wietze field, Germany. A great increase in recovery over flooding with water alone was obtained in these tests. The results may show a way to recover high-viscosity oils by a comparatively simple flooding procedure. INTRODUCTION In fields where oil recovery has not benefited from natural water drive, increased recovery may be obtained by the injection of water into the reservoir, especially in the case of fields which produce high-gravity, low-viscosity oil. There is a rather close relation between the viscosity of the reservoir fluid and the recovery that can be obtained by water flooding. As the viscosity increases the oil recovery decreases proportionately, so that an oil viscosity about 30 times that of water is generally considered to be the upper limit for an economically successful water flood.' This limitation has been recognized theoretically by Buckley and Leverett,' and has been verified by numerous laboratory flooding tests, such as by Croes and Schwarz,V n the viscosity ratio range of oil to water from 1 to 500. The reason for the inferior recovery of viscous oils by water flooding can best be understood by considering the mechanism of flood tests. In such tests water is introduced into one end of a sand-packed tube which is saturated with oil of the viscosity to be tested, and oil is produced from, the other end. Oil, with a viscosity lower than that of water, is pushed ahead of the advancing water with considerable uniformity, and irregularities in the displacement process tend to be eliminated as the oil saturation decreases and the water saturation increases. However, oil recovery is not complete, for the water forms interfaces with the oil and traps residual oil droplets in certain of the pore spaces. These residual oil droplets are distributed rather uniformly through the sand, and they are not susceptible to recovery regardless of the amount of water passed through the test cylinder. In the case of an oil possessing a viscosity greater than that of water, the injected water tends to move irregularly through the sand in the test cylinder. At the place in the sand where initial water movement takes place, resistance to the movement of water is lowered and the water finger so formed will grow perceptibly; it will extend to the outlet end of the test cylinder so that a breakthrough of water takes place long before much of the oil-saturated volume of the sand has come in contact with water. Once the breakthrough of water takes place, the water-oil ratio is gradually approaching the economic limit, even though much of the oil in the test cylinder remains unaffected by water. Disconnected drops of oil are trapped in the portion of the sand that has been invaded by water, just as when an oil of low viscosity is flooded. The poor recovery of the more viscous oils, therefore, is due to the irregularity of water movement through the test cylinder, and the rate of water movement through restricted sections of the oil-saturated sand increases with the more viscous oils. There are three ways whereby the recovery of viscous oils by water flooding can be improved:' (1) adding materials which will increase the vis-

Jan 1, 1965

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By Richard W. Markley

The predominant methods for mining coal in the USA are room and pillar and longwall. Approximately 95 percent of the coal is mined by room and pillar and 5 percent by longwall. The U.S. Department of Energy (DOE) has an ongoing program to improve the rate, quality, and cost effectiveness of stabilizing the roof for both of these mining systems. In room and pillar mining, the installation of permanent roof support is often the task which paces the system operation, and it thus controls the level of production achieved during any mining shift. Two automatic roof bolt insertion equipment developments are discussed, as well as a flexible drill for operation in thinner seams. Progress will be reported on under- ground trials of a particular flexible drill which has been combined with a bolt inserter to form a compact, reliable module for retrofitting to continuous mining machines. In longwall mining, the use of hydraulic supports on the working face provides roof stability. The DOE has several trials ongoing with shield- type supports in difficult strata conditions which are described, as well as a co-funded project with the Bureau of Mines on a resin injection remedial method for consolidating a shear zone at one site. A project to improve the match of strata conditions to shield design is also described, which involves the use of a 1360 tonne vertical load mine roof simulator.

Jan 1, 1983

By W. V. Swarzenski

In its effort to combat waterlogging and soil salinity, the Water and Soils Investigation Division of WAPDA (West Pakistan's Water and Power Development Authority) has carried out an extensive program of test drilling andwater sampling since 1954. Data collected during the past ten years have permitted the delineation of fresh and saline groundwater zones in the Punjab Plain. Fresh groundwater containing generally less than 500 ppm of total dissolved solids is found in wide belts paralleling the major rivers and in other areas of fresh-water recharge. Locally, fresh groundwater extends to depths of 1500 ft and more. Saline groundwater occurs down gradient from sources of recharge, particularly in the lower central parts of the interfluvial areas, and presumably underlies most of the Punjab Plain. The groundwaters of the Punjab are characterized by their evolution from calcium, magnesium bicarbonate waters near sources of recharge to waters containing a dominant proportion of sodium. The highly mineralized waters of the Punjab are generally of the sodium chloride type, whereas in the Dera Ismail Khan District, sodium sulfate waters predominate. The pattern of distribution of saline groundwater zones and the observed gradual increase in mineral content, down gradient from sources of recharge, can be explained best by a hypothesis stressing the process of evaporation from the water table and solution of minerals within the alluvial aquifer. In 1954, detailed groundwater surveys in the Punjab Plain were initiated by WASID, the Water and Soils Investigation Division of West Pakistan's Water and Power Development Authority. The investigations, undertaken under a cooperative agreement between the governments of Pakistan and the United States, were aimed at the formulation of reclamation measures to improve waterlogged and saline soils, and to assess the groundwater potential of the Punjab and other areas of West Pakistan. The nature and urgency of WASID's primary task limited the exploration of the alluvial aquifer generally to its uppermost part. About 1030 test holes drilled in 47,000 sq miles of the Punjab defined the nature of the alluvium to depths of about 600 ft and yielded data on water quality to 400 or 500 ft. A report on the hydrology of the Punjab, based on the results of these investigations was published by WASID in 1963.' The present report incorporates data obtained by WASID since 1962 in a program of deep test drilling in the Punjab and the adjacent areas of Bahawalpur and Dera Ismail Khan District, permitting the definition of fresh and saline groundwater zones to depths of 1500 ft in some areas. Groundwater in the Punjab Plain is contained in alluvial deposits, predominantly sand and silt, which extend almost everywhere to depths of 1000 ft and more. The alluvium has been deposited by the Indus River and its tributaries since late Tertiary time and is contiguous with similar deposits in India. The Indo-Gangetic Plain extends from the foothills of the Himalayas to the ancient rocks of the Peninsular Shield in central India and to the ocean. Gradients are generally very low and range from about 1% ft per mile in the upper part of the plain to less than 1 ft per mile in the south and southwest. The monotony of the alluvial plain is broken by scattered bedrock outcrops in two of the interfluvial areas, Chaj Doab and Rechna Doab. The bedrock hills are projections of the northwest-trending Delhi-Shahpur Ridge that is largely buried by alluvium. The rocks of the buried ridge, presumably of Precambrian age, are essentially impermeable and define the lower limit of the alluvial aquifer in parts of Chaj, Rechna, and Bari doabs. Elsewhere in the Punjab, there are no outcrops of other consolidated rocks and their presence below the alluvium is conjectural. The principal areas of bedrock outcrops, near Kirana and Sangla, are shown diagrammatically in Fig. 1. The movement of groundwater through the alluvial aquifer of the Punjab has been described by Green-man and others.' In most of the area, the pre-irriga-tion water table sloped from the rivers downstream and toward the central axes of the doabs, indicating that the rivers were sources of groundwater recharge. As a result of seepage from irrigation canals, water levels have risen as much as 90 ft. In 1960 they were within 5 to 15 ft of the land surface and above the

Jan 1, 1970

By A. F. Giamei, E. J. Freise

A discussion of the various factors affecting the accuracy of volume fraction determination by the direct comparison X-ray diffraction method is presented. To minimize errors introduced by nonrandomization effects such as preferred orientation and large grain size, as well as errors introduced by statistical effects, an iterative mathematical analysis is introduced. This analysis is applied to all observable diffractio~ spectra from a given specimen by means of computer techniques and is statistically superior to the standard direct comparison technique which utilizes only one or tm sets of intensity spectra. The computer program also presents a graphical interpretation of- the results which enables the investigator to visualize and readily assess the scatter in volume fraction estimates caused by deviations from randomness. Finally, the iterative analysis is applied to experimental data collected from a series of plain carbon steels in both the as-received and spheroidized conditions to determine the volume fraction of cemen-tite present in each case. The results show markedly good agreement with chemical analyses for all spheroidized specimens. In theory, quantitative X-ray diffraction is a power-ful analytical technique for precise determination of the volume fractions of various phases present in a multiphase poly crystalline aggregate. There are two generally used methods; both utilize the fact that the intensity of a diffraction line of a particular phase is a function of volume fraction of that phase present in the aggregate. The more common method is the so-called internal standard technique where a known amount of standard substance is mixed with the aggregate containing the unknown. The resulting ratio of the intensity of a particular diffraction line of the unknown to the intensity of a diffraction line from the standard is used to find the weight fraction of unknown material by reference to the intensity data obtained from a previously prepared set of standards containing the same amount of standard material. The details of this technique are outlined in standard works on X-ray diffraction.' The disadvantages of the technique are that it requires the use of powder specimens and that the powder mixture must be homogeneous near the surface to the maximum effective beam depth. The alternative technique is the direct comparison method in which the ratio of the intensity of a diffraction line of a phase in the aggregate to the intensity of a second-phase diffraction line yields the ratio of the volume fractions of each phase present. This method has been applied most extensively to the determination of the percentage of retained austenite in martensitic steels and to determining the amounts of hcp and fcc allotropic modifications in pure cobalt5 and the amounts of hexagonal and rhombohedra1 modifications in graphite.8 This method is applicable to bulk as well as powder aggregates and is the technique which will be considered in the following text. It is the purpose of the present communication to show that by combining the results of X-ray diffrac-tometry with the use of high-speed digital computers the results of the direct comparison quantitative X-ray analysis technique can be optimized by using all of the data available on a diffraction pattern. THEORETICAL DISCUSSION In optimizing any quantitative X-ray diffraction experiment, the problem of accuracy vs time to collect and analyze the experimental data arises. For any method to be practical, it is required that both experimental and analytical procedures are reasonably short. In most of the previous work performed by the direct comparison method, intensity data from only one or two sets of peaks were used to calculate the volume fraction of phases present in the aggregate. Consequently, rather long-time experimental measurements are required to assure that the intensity data are sufficiently accurate to justify the use of one or two sets of data. By using computer techniques to analyze the experimental data it becomes feasible to use all of the available data on a diffraction pattern. By so doing, the time spent in measuring any one diffraction maxima can be appreciably reduced. Although this results in poor counting statistics for any one maxima, the number of data points available for analysis is greatly increased. Based on the above discussion, it will be assumed that a continuous scanning counter-diffractometer technique will be used to collect intensity data from a two-phase mixture. The integrated intensity of the ith diffraction line from the a phase in the aggregate is given by:'" where is the volume fraction of the a phase, The various quantities in Eq. [la] are angular independent while those in [lb] depend on the hkl spectrum of a particular phase. The meaning of the individual quantities in Eqs. [la] and [lb] are given in Appendix 1. It is convenient at this point to outline briefly the factors which will affect the measured intensity of any one hkl spectrum. a) Extinction effects arise from two independent experimental conditions. Primary extinction arises from a high degree of crystal perfection and results in spectra having lower intensity than predicted by Eq. [I]. Any treatment, such as powdering, which reduces

Jan 1, 1968

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By J. A. Reeves

The unit-train for moving mineral raw materials is considered by many railroad men as the most significant contribution toward reducing rail freight costs since the introduction of the diesel locomotive. The idea, which involves assigning railroad equipment to only one haul and keeping the equipment rolling, results in the maximum utilization of equipment. For example, before the unit train was placed in service on coal hauled to one of Mid-Continent Coal and Coke Company's customers, about 900 cars and 9 locomotives were needed to move its coal requirements, compared with 250 cars and 6 locomotives currently used. If unit-train economics are to be achieved, coal companies cannot use railroad cars as small storage bins on wheels to accumulate their coal in train-load shipments, instead, these companies must build large bins which incorporate facilities for the rapid loading of railroad cars in a minimum length of time.

Jan 1, 1970