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By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of 'twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967

By Robert L. Voss, Richard D. Hagni

Sparry dolomite from all of the operating mines in the Viburnum Trend of Southeast Missouri have been found by cathodoluminescence microscopy to reveal a systematic pattern of banding resulting from a growth zoning within individual dolomite rhombs. Four principal bands have been recognized throughout the entire Trend and each of the major bands contain even finer internal banding. Minor bands a few microns in width can be correlated in specimens collected ten's of kilometers apart along the trend. The first three principal dolomite bands decrease from south to north. This feature, together with the fact that the white sparry dolomite crystals decrease in abundance from south to north in the Trend, suggests that a major source for the fluids was from the south. The application of cathodoluminescence microscopy to crystalline dolomite demonstrates a strong correlation between ore grade and the intensity of internal banding and dissolution textures.

Jan 1, 1985

By R. P. Aikman, F. G. Miller, J. M. Podgursky

In response to the growing demand for low-sulfur coking coal for iron-making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, (i.e., +28 mesh) at almost any desired specific gravity. However, in the case of fine coal (i.e., -28 mesh) neither of the two existing processes-froth flotation and hydrocycloning-in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this article is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods.

Jan 7, 1967

By H. O. Hofman

Lime-roasting is a term proposed by Ingalls' for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse un-decomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale,—the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent. of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1908

By Ray W. Amstutz

The shaft was drilled on US government land m the Piceance Creek basin and was funded by the US Bureau of Mines (USBM). It was drilled to 723 m to provide access to rich deposits of oil shale, nahcolite, and dawsonite for geotechnical test work and environmental mining research. Rotary drilling and dual-string, reverse-air, jet-assist circulation methods were used. Drilling required eight months. Site preparation, running, and cementing the casing required another four months. A 2.44-m ID steel welded casing, 508 mm thick was installed and 2.7 kt of cement were slurried and pumped into the annulus.

Jan 1, 1982

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By J. H. Frye, D. L. McElroy, E. E. Stansbury

The rates of growth of pearlite in high-purity Fe-C alloys have been measured as a function of the transformation temperature. These and other data have been correlated in terms of a derived rate equation. Activation energies for the growth were found to be 24,200 cal per mol of austenite for the 0.78 pct C alloy and 27,600 cal per mol for the 0.93 pct C alloy. Theoretical implications are discussed. AN excellent review of the the theoretical and experimental studies on the mechanism and kinetics of the eutectoid reaction has been presented recently by Mehl and Dube.' They have pointed out that these investigations have followed two lines of approach: 1—experimental studies and derivations of expressions for the overall transformation characteristics, and 2—derivation of expressions for the nucleation and growth rates in terms of fundamental processes. Investigations of the latter type have been concerned for the most part with the nature of the growth at the austenite-pearlite interface in plain carbon and alloy eutectoid steels. They discuss two theories of the rate of growth of pearlite from aus-tenite—those of Brandt and of Zener. Both derive rate equations which are based on the assumption that carbon diffusion is the controlling mechanism. Mehl and Dube,' Zener,2 and Brandts. " have attempted to calculate growth rates by use of these equations together with thermodynamic and diffusion data. The results are encouraging, but agreement is not so good as to constitute verification of the theories. Furthermore, it Is not clear how these equations are to be used to study the effect of alloying elements which apparently exert little influence on carbon diffusion, but markedly decrease growth rates. It is not clear whether or not the addition to iron of an alloying element which does not diffuse during transformation can alter the rate of growth of body-centered from face-centered cubic iron. That it can greatly decrease the overall transformation rate has

Jan 1, 1954

By Claus Guenter Goetzeil

(New York Meeting, February, 1937) The object of this investigation was to determine whether silver alloys could be used instead of the currently employed insert of high-expansion Average Coefficient per Deg. C. over Range 20° to 200° C. Pure aluminum..................................... 24.6 X 10-6 Cast low-expansion Si-Cu-Ni-A1 piston alloy............ 20.0 X 10-6 High-expansion austenitic Cu-Ni cast iron.............. 19.3 X 10-6 Cast steel (0.25-0.35 C, 0.40-1.0 Mn).................. 12.6 X 10-6 Cast iron (3.15 total C, 2.16 Si)....................... 12.8 X 10-6 Pure silver.......................................... 18.9 X 10-6 austenitic ferronickel alloy, to reduce the wear of ring grooves in light metal pistons. A typical example of a piston containing a ferronickel insert is shown in Fig. 1. The high coefficient of expansion of silver made it worthy of consideration, while the small size of the insert would render its use feasible in Germany as an emergency measure. The coefficients of linear expansion of several metals and ailoys are as shown in the table above. Obviously the melting point of the insert must be high enough to prevent it from melting when the light alloy is cast around it. This imposes a lower limit of about 850" C. for the solidus of the silver alloy. Pure silver melts at about 961" C., so that the tolerable depression in the solidus is rather small. To avoid deformation of the insert during use a Brinell hardness number of at least 60 appears necessary.

Jan 1, 1937

By R. V. Higgins, A. J. Leighton

A fast method is needed for calculating thoroughly the performance of two-phase flobr~ in reservoir rock with complex geotrietry. The authors present such a method and .slzow its accuracy by romparison with laboratory performrrnce of a five-spot pattern. In making the performance c.alculations, the octant of the five-spot pattern was divided into four channels. The computer tinle required for the culculation was one rllinrcte. This is rorighly about minute per channel. INTRODUCTION By using an electronic computer it is now possible to make reservoir performance calculations in which fewer assumptions and more significant variables are included than was possible with a desk calculator. These performance calculations include such variables as the properties of the reservoir rock and its contained fluids, properties of the rock-fluid system and even different well-spacing patterns. Usually, the more variables that are included the higher the computer cost—and time on the computer is expensive. As a result, a short procedure is needed so the many variables will be included and accurate performance calculations will result. If a reservoir is composed of alternate layers of permeable and impervioi~s rock, and if each conducting layer has a different relative permeability, the combined computer cost for calculating each layer by the present long computer programs (which includes different well-spacing patterns and other variables) would be expensive. The performances of complex spacing patterns in a field often are studied by a potentiometric model, but in these model studies the analogy is to the flow of only a single phase. This paper presents a procedure to calculate the performance of a five-spot pattern with two phases flowing using a potentiometric model as a guide for the dimensions of channels and other related data. The time required to calculate the complete performance is about one minute on the IBM 7090 or four minutes on the IBM 704. The procedure can be extended to calculate the performance of more complex well spacings or an entire field with little modification. The procedure has been tested on the performance of the laboratory water floods of a five-spot pattern reported by Douglas, et alThe range of viscosity ratios in the laboratory experiments is from 0.083 to 754, which is extensive. The accuracy of the performance calculations is excellent as shown by the plotted points in Fig. I. The recovery as influenced by the geometry of the five-spot, taking into account the deviation from true radial character, has been predicted by Aronofsky and Ramey." The authors used a potentiometric model to determine the sweep efficiency to breakthrough of the flooding agent. Dyes, Caudle and Erickson,' by means of a laboratory model, show the influence of mobility ratio on recovery after breakthrough of the injected material. Dyes, et ai, used the X-ray shadowgraph technique and miscible phases in their studies. Craig, Geffen and Morse from the analysis of the performance of their laboratory model correlate many variables, including average saturation of a flooding agent determined by permeability relationship. Craig, et al, used X-ray shadowgraphs to determine the sweep efficiencies in sandstone models. In this report the sweep efficiency is not needed, and the important effect of continuously changing saturation gradients before and after breakthrough

By William A. Hustrulid

INTRODUCTION Prior to the mid-1970's, the U.S. Radioactive Waste Disposal Program was focused on salt deposits as the geologic medium of choice, almost to the exclusion of other rock types. These efforts are illustrated by the Project Salt Vault experiment in a salt mine at Lyons, Kansas, in 1965-1967 followed by attempts to locate a repository site in central Kansas. Preliminary evaluation of other geologic media led, in 1978, to the GAIN (Geotechnical Assessment and Instrumentation Needs for Nuclear Waste Isolation in Crystalline and Argillaceous Rocks) Symposium held at the University of California (Berkeley), for the purpose of preparing a state-of-the-art document together with research needs for some of the other possible rock types. Because possible sites had not been selected, nor would they be for some time, the primary emphasis was for research and development focused on generic rocks and generic sites. A basic ground rule at that time was that the host rock formation should provide the primary containment for the waste. Also, the U.S. Nuclear Regulatory Commission (NRC) was just drafting the proposed rules regarding site suitability so that this input was not available. The collection of baseline data, conduction of some critical experiments both in the laboratory and field, and the performance of scoping studies were deemed needed. Such work was indeed undertaken; and to date, a great deal of information has been compiled and much has been learned regarding the characteristics of rock masses, rock behavior

Jan 1, 1984

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By H. J. Rose

The peak of production from the Appalachian natural gas field was apparently reached about 10 years ago, and the annual production from Pennsylvania, West Virginia and Ohio has now dropped to about two-thirds of the amounts obtained in 1916 and 1917. This falling off in production has occurred in spite of vigorous efforts and large expenditures by producing companies to maintain or increase their output. The greatly increased costs of development and handling are reflected in the present average value of natural gas at the point of consumption, which value in the three states referred to has more than doubled in the past 10 years. While it is true that the natural gas production of the United States has increased during recent years, this increase has come from southwestern states, particularly from Oklahoma, California, Louisiana and Texas, which states are now leaders in the production of this valuable but fleeting resource. Pennsylvania, originally the leading state in natural gas production, occupies sixth place in the latest (1924) U. S. Bureau of Mines statistics. West Virginia, which held first place for 15 years, has dropped to third rank, and Ohio is the seventh state in the order of natural gas production. Domestic and industrial demands for gas are constantly increasing everywhere in the United States. These growing demands have accentuated the difficulties in the localities with depleted natural gas supplies, and serious shortages have already occurred during winter months in the Pittsburgh district. Some relief has been obtained by placing restrictions on the industrial use of natural gas, and by increasing the price (which tends to reduce consumption). Yet these are but temporary expedients for checking gas consumption, which fail to solve the problem of adequate future supplies of gas. Gas is an exceedingly valuable and important form of fuel, and serious restrictions on its use cannot be tolerated for long in any community. As the supply of natural gas declines, it must be supplemented and eventually replaced with some form of manufactured gas. Many cities, including Pittsburgh, are already supplementing their natural gas supply with the manufactured product.

Jan 1, 1930

By W. K. Lewis

During the last decade the petroleum refinery engineer has made great progress in achieving a better understanding of the physical behavior of hydrocarbon mixtures, with particular reference to their pressure-temperature-volume relationships, the mechanism of the evaporation of liquids, the condensation of vapors, including the changes in composition, and the heat effects accompanying them. With the new insight into the mechanism of movement of oil and gas through the formations in which they occur, achieved by the production engineer, it is clear that the latter will need to utilize in the solution of his own problems much of the information outlined above. It is the purpose of this paper to outline the portions of that information that seem most certain to prove of importance in production work. Properties of Pure Hydrocarbons While it is true that petroleum always consists of highly complex mixtures of hydrocarbons, none the less understanding of the behavior of the mixture must be based upon a knowledge of the properties of the pure components. However, in view of the tremendous number of hydrocarbons existing in petroleum, the determination and formulation of the properties of all of them would seem a discouraging task. The difficulty of the situation is increased by the undoubted facts that the overwhelming majority of chemical individuals in petroleum have never been isolated as pure compounds, none of their physical properties have been determined and even their chemical constitution is unknown. The situation would be hopeless were it not for the fact that certain extraordinary correlations of important properties of various hydrocarbons have been discovered which make it possible to predict those properties for a given chemical individual on the basis of a very limited characterization of it. Thus one can predict the vapor-pressure curve of an unknown hydrocarbon over a considerable range from the knowledge of a

Jan 1, 1934

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By K. Huessener

Discussion of the paper of K. HUESSENER, presented at the New York. meeting, February, .1916, and printed in Bulletin No. -110, February, 1916, pp. 443 to 474. KARL NIBECKER, Youngstown, O.-It has been contended that the method of measuring the operation of a blast-furnace boiler plant by means of the amount of steam generated per pound of coke used in the blast furnace is not of any value and even that it is quite misleading. It has been found, in the plant with which I am connected, that, in general, a blast furnace will operate during a month so close to average. conditions that the average monthly measure of the plant efficiency is indicated by the number of pounds of steam made per pound of coke put into the furnace, neglecting the amount of iron made and the amount of gas used for heating the stoves. For some time, it has been our custom to keep a record of this figure and use it as a general indicator of the operating practice. In comparing this figure from two different plants we have found some difficulty, due to differing conditions. It is conceivable but not altogether probable that a slight difference in burden, kind of ore or coke, would account for this difference. The method of using the gas, whether washed or unwashed, and the plant arrangement, may affect this number. For several plants on which we have worked up this number, we have found that most of the ordinary running irregularities are eliminated during a run of a month or more and that the number is, therefore, satisfactory. In connection with a plot of the number of pounds of steam generated per pound of coke, we are also plotting the production of the furnaces and the pounds of coke used per ton of production. With these three curves plotted on the same sheet, we believe that the operating man has sufficient information to judge of the efficiency of his plant' for any month.

Jan 5, 1916

By B. E. Grant

There are several exceptions from the practical operating viewpoint that might be taken with the paper. The author recommends using a "curve" in plotting safety factors of ropes and suggests that the U. S. Bureau of Mines change its present "step curve" method to the "curve" method. From an engineering theoretical point of view that is possible, but from a practical standpoint it is not possible. Rope manufacturers fabricate their ropes in diameter gradients of 1/16 in. to 1/4 in. which automatically sets up a step pattern gradient. If ropes were manufactured in the diameter gradients of 1/1000 of an inch or thereabouts, the curve method could be used. Also, from a practical standpoint, if an operator is to hoist from a depth of 4000 ft, for example, he will determine the size of the rope necessary for that depth, and it is only natural that he will have safety factor to spare at lesser depths, and in plotting this excess capacity the natural end result is a curve. The U. S. Bureau of Mines tables are set up so that the operator will know what size rope at the required safety factor he will need at his maximum depth. He is not concerned with lesser depths. W. A. Boyer (author's reply)-Mr. Grant states, "Rope manufacturers fabricate their ropes in diameter gradients of 1/16" to 1/4" which automatically sets up a step pattern gradient." There is no connection or relationship between the "size" pattern gradient and the present "factor of safety" step pattern gradient. The inherent factor of safety values for any particular size of rope with a given connected load when plotted for various depths is a curve, and with modern rope material and construction the inherent factor of safety curve is quite far removed from the present recommended factor of safety step curve. This is shown quite clearly in Figs. 3 and 4 of my paper.

Jan 11, 1954

By Henry Phelps Howland

During the last decade no topic has created more interest or received more thought among blast-furnace men than coke. One reason for this is, undoubtedly, the remarkable increase in the use of byproduct coke. Formerly our coke was made at a distance from the furnaces and by a distinct organization. There was little cooperation or development possible under these conditions. Today the situation is greatly changed. Much of our coke is made by the organization operating the furnaces and the coke oven is operated with the primary object of obtaining the best results in the blast furnace. The effect of changing the method of coke manufacture, even in some minor detail, is often felt almost immediately at the blast furnace. There naturally results one of the most valuable assets of the byproduct coke oven, i.e., the possibility of increased blast-furnace efficiency due to close observance and correct operation of the ovens. The results are evident, but often it is difficult correctly to account for them. In attacking the solution of a problem of as much importance as why one coke is better than another, there are facts which should be kept clearly in mind. The author hopes, in this paper, to bring out some points relative to the use of carbon in the blast furnace which will be of value in solving this question. GeÜner's Ideal Working Years ago GrÜner made a statement regarding the use of carbon in the blast furnace, which has been very generally accepted by metallurgical and blast-furnace men. I quote this theory as given by Prof. Richards on p. 248 of Metallurgical Calculations: "From the standpoint of the generation of the maximum quantity of heat in the furnace, GrÜner was right in formulating his dietum of the ideal working of a blast furnace, vie.: All the carbon burnt in the furnaee should be first oxidized at the tuyères to CO and all reduction of oxides above the tuyères should be caused by CO, which thus beeomes Co2."

Jan 1, 1917

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By Harry Seltz

SEVERAL investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeser1 has made measurements of "average heat capacities" of iron carbide between 1026° and 85° K., using a water calorimeter. His computed true specific heat at 78.1° K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0° K. The cementite used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes" has measured the specific heat of iron carbide, from 102° to 323° K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100° K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3C, S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley' has reviewed these measurements and calculations, and selects those of Roth4 and Naeser5 as worthy of most consideration. Roth has given ?H = 5400 cal. ± 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (ß) he finds OH = 5600 cal. Kelley accepts the rounded figure ?H = 5500 as the heat of formation at 298.1° K., but this value is quite uncertain.

Jan 1, 1939

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964