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By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By G. O. Prickett, P. Somasundaran

An experimental progmm based on statistical principles is used for optimizing a flotation operation for the separation of minerals. In this case, flotation of sylvite from sylvinite ore with amine and starch as the flotation reagents was studied to find the optimum reagent levels at various slime levels. The experiments were first done on a two-level three-factor design. Analysis of the results showed that the interactions between various factors were significant. Hence, a first-order linear model of the flotation response would not be accurate. The two-level three-factor design was expanded into a composite design in order to test the fit of a higher-order model. Data were treated to obtain an expression for flotation response as a function of the different variables, to predict the optimum reaaent levels at various slime levels, and also to determine the path of steepest ascent. Tests around the predicted optimum and along the path of the steepest ascent were done until a near-optimum region was obtained. Exploration of the nature of the response surface in that region established the actual location of the maximum response. The optimum amine level was found to be 0.20 lb of amine per ten of ore at all slime levels, while the optimum starch level varied as a function of the slime present. Computer access at the laboratory by means of a teletype terminal on a commercial time-sharing system enabled efficient and accurate treatment of experimental data. The efficiency of experimental investigations can be improved significantly by the use of experimental design and data analysis based on statistical principles. The common approach used in experimental research is to study a property of a system as a function of "one-variable-at-a-time". Several authors'-4 have pointed out the inadequacy and deceptiveness of this method. Results obtained for the effects of a variable on the measured response of the system using

Jan 1, 1970

By Nicholas Kowall, K. L. Clark

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By K. L. Clark, Nicholas Kowall

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By J. Clair, H. Mirabel

The determination of the temperature and electrical potential distributicms in the cathodes of aluminum electrolytic cells is difficult. The reascms come from the various nature and the intricate three-dimensional geometry of the materials; besides thermal and electrical phenomena react upon each other. A method of calculation using a computer program applied to a mathematical model, figuring the cathode, is developed. Both of the thermal and electrical phenomena are simultaneously considered. Temperature and electrical potential distributions are finally obtained by successive iterations. Results are compared with measurements on industrial cells. Theoretical and practical applications of these studies are given. Up to the present time the study of the distribution of the temperatures and electric potentials in the electrodes, anode and cathode, of the electrolytic cells used for the production of aluminum was limited to one of the two aspects of the phenomena because of lack of a simultaneous method of calculation. For example, the anode or cathode drop was studied assuming that the temperatures in the iron and carbon are known, a method that obviously is very approximate since iron resistivity, in particular, greatly varies with temperature, which in turn depends on current density. Consequently we tried to find a method of calculation simultaneously taking into account both thermal and electrical phenomena. We proceeded to the study of the cathodes as an initial approach to the problem. Although the cathode and surrounding materials may have varied forms and particularly very heterogeneous characteristics, their structures are simpler than that of the Sijderberg anode and boundary conditions are more easily represented than in the case of anodes even though they are prebaked. The study was in two parts: a) development of a model schematizing the true geometry of a cathode and defining the thermal and electrical boundary conditions, and b) working out a method of calculation of the temperatures and potentials by means of an electronic computer. To facilitate solution of the problem, a model was used initially much simplified in comparison with an actual cathode. This model permitted development of the method of calculation. In a second phase, this model was adjusted to the study of actual cathodes and applied to different types of cells: low- or high-intensity cells, cells set up at ground level or above ground level, cells with cathodes more or less heat-insulated. Simultaneously measurements were made with cells equipped with cathodes of the types studied to compare the values resulting from calculation. The initial model was also used for general studies, in particular for studying the effects of current density in the carbon and iron. The results were confirmed or made precise by the model of the true cathodes. This report successively describes: a) the manner in which the model representing a cathode was worked out, with the simplifications and/or the hypotheses used, b) the method of solution of the problem by means of the electronic computer, and c) an example, stating the extent to which the results obtained may be realistic. Further the possibilities offered by such a study are examined. 1) CATHODE REPRESENTATION The purpose of this phase is to represent the cathode in the form of a so-called "mathematical model", that is with a simplified geometrical configuration, in order to meet the subsequent calculation requirements, while keeping to the true facts as closely as possible. This model further includes the thermal and electric conductivities with regard to temperature for the varied materials composing the cathode, as well as the thermal and electrical conditions at the model boundaries. 1.1) Guiding Principles. For calculating the temperatures and potentials the model is divided by trior-thogonal planes into a network of small elementary parallelepipeds. At the summit of these parallelepipeds' so-called mesh points, the temperatures and potentials are computed. The number of mesh points is of course limited by the capabilities of the computer, since 1) the number of equations to be solved depends on the number of mesh points selected, and 2) the amount of time spent by the computer considerably increases with increasing this number. These conditions call for the following requirements as concerns the model: a) Dimensional requirements: the calculation will be all the more accurate as the network is more closely meshed. Since the number of mesh points is limited in practice, it is necessary to restrict the dimensions of the model. b) Geometrical requirements: so as to make things easier in working out the network, the model must be given a simple geometry. In particular, it will be convenient to have the cathode so constituted that the surfaces limiting the cathode and the surfaces within the cathodes separating the different materials consist of triorthogonal planes. 1.2) Schematization of the Cathodes. After the tech-

Jan 1, 1968

By J. V. W. REYNDERS

IN THE remarks which I am about to make concern¬ing the safety work of the Bureau of Mines, I want first of all to disengage myself from a disposition, which is frequently in evidence, to give spectacular emphasis to the hazards of mining operations. It is of the' utmost importance to the industrial welfare of our country that the enormous annual requirement of fuel be produced and be made available in our economic activities, with a minimum of distress and hardship. The safety of coal mining is a condition with which. we are all concerned in a fundamental way. And yet we should not rush to accept hastily conceived notions that laxity among employers in respect to safety measures exists to any outstanding degree. In fact in a large number of instances, the precautionary efforts of min¬ing companies, directed to the elimination of accidents are beyond all criticism, albeit the industry suffers in reputation from the carelessness of, its less effi¬cient constituents. The Bureau of Mines has been a leading influence in disseminating the doctrines of safety, in securing the cooperation of the miners themselves, and in stirring up ' the laggards, both among the employers and the employed. It is much to the interest of well-conducted mine operations that the industry, as a whole, observe safety regulations to the utmost.

Jan 1, 1925

By E. W. Enqelmann

DURING January, 1933, burlap or coco matting was placed in the bottom of launders handling various products of the flotation plant of the Magna mill of the Utah Copper Co., with the hope of increasing the total recovery of gold. This was soon followed by placing various materials, such as coco matting, cotton twill, and common 10-oz. burlap on the bottom of the main tailing launder. The burlap was found to be the most economical material to use. The test was first conducted in an old wooden launder, 40 in. wide and 2000 ft. long, with 10-oz. burlap fastened

Jan 1, 1935

By Joseph Pogue

THE writer visited the Muzo emerald mines in July, 1915, and spent six days in their study. This paper embodies the results of his observations, plus information personally communicated by Robert Scheibe, FIG. 1.-SKETCH MAP SHOWING APPROXIMATE LOCATIONS OF ALL IMPORTANT EMERALD MINES AND PROSPECTS IN COLOMBIA. (Data in part supplied by Robert Scheibe, July, 1915.) Professor of Geology in the Mining Academy of Berlin, who at the time of the visit was completing a detailed field investigation of nearly a year's duration of the emerald deposits of Colombia. An elaborate account of this valuable work may be expected at a future date from the pen of Professor Scheibe.

Jan 5, 1916

By Roscoe C. Clark

In a previous technical note' by Walter Rose, evidence is offered in support of the contention that "the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely." It is not the purpose of this note to present further discussion of this possibility but rather to point out that the argument presented there does not appear to be generally valid. In the cited note' reference is made to the experiments of Welge2 wherein it was shown that when water was displaced by oil from a core the pressure in the water phase was less than in the oil phase but that when this oil was then produced by water drive the pressure in the water phase was greater than in the oil phase. Rose has concluded from these observations that conditions of static equilibrium did not obtain since the fluid saturations were such that phase discontinuities seemed unlikely. The argument from which this conclusion was drawn is based on the contention that "the pressure is always greatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase." This premise appears to have been reached from a consideration of capillary phenomena in cylindrical tubes, although it may a1so hold for other types of pore geometry, hut as will be shown below it does not hold for all pore shapes and hence is not generally applicable. Since the pore structure of porous media such as reservoir rocks i- in general so complex as to defy exact description. it is undoubtedly of great value to establish a model in terms of pore shapes of known geometry, provided of course that the limitations of the model are recognized. That the limitations of the capillary. or cylindrical, tube model have not always been fully recognized will be evident from the following discussion of a pore of different shape hut one which may a. logically he considered a.; the capillary tube. The pore space to be considered is that shown in Fig. 1, which may be thought of as the "hole in a doughnut."* Consider the interface, A-B-A', between two immiscible fluids, P, and P2, which interface meets the solid alone a line, A-C.A'-C'. The interface A-B-A' is the surface of a spherical segmen† while the line of mutual contact be-

Jan 1, 1950

[Trans. No. Place Date Vol. Page 1, Wilkes-Barre, Pa.* .... May, '71.. 1 3 2. Bethlehem, Pa Aug., '71.. 1 10 3 Troy, N. Y Nov.,'71.. 1 13 4. Philadelphia, Pa Feb., '72.. 1 17 6. New York, N. Y •.... May, '72.. 1 20 6. Pittsburgh, Pa..:.Oct., '72.. 1 25 7. Boston, Mass Feb., '73.. 1 28 8 Philadelphia, Pa.' May, '73.. 2 3 9. Easton, a Oct., '73.. 2 7 10. New York, N. Y Feb., '74.. 2 11 11. St. Louis, Mo.* May, '74.. 3 3 12. Hazleton. Pa Oct.. '74.. 38 13. New Haven, Conn Feb., '75.. 3 15 14. Dover, N. J.' May, '75.. 4 3 16. Cleveland, 0 Oct., '75.. 4 9] [ ]

Jan 1, 1925

By R. A. Ritter, J. P. Batycky

A numerical technique has been developed to permit estimating the pressure gradient associated with laminar flow of thixotropic liquids through long Pipelines. For this purpose the pipeline is divided into a number of radial and longitudinal increments within which rheological properties of the fluid may be considered as constant at any time. Then, provided only that the fluid flow curve is defined at every duration of shear, it is possible to predict the instantaneous pressure gradient at any cross-section along the pipeline for each desired flow rate and pipe size. The technique consists of an iterative integration of shear rate to establish the appropriate value of the wall shear stress at each location. Consistency of fluid in the increment is determined by the flow history of that increment, while the radial flow associated with variations in velocity profile is accounted for by adjusting the width and radial position of the increment. A number of pressure profiles, computed at each of several flow rates, provide a convenient basis for pipeline design and pump selection. INTRODUCTION In recent years considerable attention has been given to predicting pressure drop associated with the isothermal laminar flow of time-independent non-Newtonian fluids in pipes and annuli. 6,11,12 The approach generally has been to develop analytical relationships between flow rate and pressure drop based on simple constitutive models which hopefully provide an approximate description of the rheological properties of the fluid. Analytical solutions are highly desirable since the influence of all pertinent parameters can be readily determined. Unfortunately, however, this approach is restricted to simple flow geometries and- frequently leads to erroneous results due to inadequacies in the model. In certain cases a solution may be obtained through applying appropriate numerical techniques.l,14 For example, a digital computer program is available for predicting the velocity profile and pressure drop encountered by any Newtonian or time-independent non-Newtonian fluid flowing under laminar conditions in a cylindrical pipe or annulus.l In this paper the consistency behavior of the fluid need only be described in terms of basic rheological data. Analyzing flow systems involving fluids with time-dependent rheological characteristics is considerably more complicated since substantial changes in consistency may occur because of sustained shear action. This sensitivity to shear frequently persists for several hours. Consequently, variations in pressure drop and/or flow rate resulting from the aging process and addition of unsheared or partially sheared fluid to the system must be considered for purposes of pipeline design. This paper outlines a numerical method for predicting the transient and steady-state laminar flow behavior of a thixotropic liquid in a pipeline of arbitrary length (i.e., at a specified constant flow rate, the instantaneous pressure gradient may be determined at any time after start up and at any location along the pipeline). Several such pressure gradient profiles, computed at several flow rates, may be combined to produce a complete portrait of the system response. This flow portrait provides a reasonable basis for pipeline design and for selecting a suitable pump characteristic. TIME-DEPENDENT RHEOLOGICAL BEHAVIOR The most familiar time-dependent rheological properties are those exhibited by thixotropic liquids. Many of these materials, particularly thixotropic crude oils, generally display an apparent yield stress in that a finite pressure gradient is required to initiate flow. Then, under the influence of sustained shear at a constant shear rate, the consistency systematically decreases to some final limiting value. The shear stress obtained at

By L. A. Schrider, J. A. Wasson

A method of predicting waterflood performance has been developed that combines certain facets of several previously published prediction techniques. The manner of combination has required the development and use of some new and some little-known relationships and has eliminated several of the weaker assumptions inherent in the original individual prediction methods. This approach, which was designed for computer solution, has removed the necessity of referring to plotted curves and permits the analytical prediction of water flood performance for a five-spot well pattern in either homogeneous or stratified reservoirs. The Predicted values are expressed in common oilfield units rather than in abstract or dimensionless terms. The calculation procedure has been programmed in FORTRAN IV and the entire program listing is available to potential users.* Introduction Prior to initiation of secondary recovery of oil by waterflooding, the possibilities of economic success or failure must be evaluated with the greatest practical accuracy. Although many prediction techniques are available, most, if not all, have serious limitations. In recent years, the Bureau of Mines has attempted to stimulate interest in the secondary recovery of oil from Appalachian pressure-depleted reservoirs. Waterflooding, because of its widespread acceptance and success, is the principal secondary-recovery method considered. During the life of the project, several performance prediction methods have been studied and applied. Because these methods, individually, have inherent assumptions and limi-tations, portions of some of them have been selected and combined in an effort to eliminate such shortcomings wherever possible. We believe that the resulting technique is as accurate as the necessary available data will permit and that it has several distinct advantages over previously published methods. Development of the Method The fractional flow equation developed by Buckley and Leverett' from Darcy's law is the fundamental mathematical statement describing immiscible fluid-fluid displacement in porous media. A generalized form of this relationship, whose derivation is readily available in the literature, is The formation dip, a, is usually very small in those petroleum reservoirs being considered for pattern waterflooding in the Appalachian area. Therefore. in many cases. a has an almist negligible value. In addition, Ap, the difference between the density of water and the density of oil, is relatively small. For these reasons the gravitational term may often be neglected. Capillary pressure is a function of saturation, which is in turn a function of distance from the upstream boundary of the system or the injection well. In this study it is assumed that the frontal zone of the waterflooding (or zone of capillarity) has negligible length and that only those saturations in the water-swept zone at breakthrough and later are of interest. As the distance in a waterflood pattern is comparatively large and the change in water saturation with distance is usually small, the change in capillary pressure with distance is negligible. The simplified form of the fractional flow equation is appropriate, therefore, in this application. Three variables must be considered in determining that fraction of the total fluid flow that consists of water: the viscosity ratio, saturation, and relative permeability ratio.

Jan 1, 1969

By H. Hubert

THE first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lürmann and to Lencauchez, who had pointed out the blast-furnace as a powerful -gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgow Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Nov 1, 1906

By Mark Malamphy

DURING colonial times, Brazil was famous for the richness of her alluvial gold deposits. Paul Ferrand has estimated that the gold produced during the period from 1700 to 1820 was the equivalent of some 64 million pounds sterling. Since that time, most of the more prolific alluvial deposits have been exhausted. A few gold mines are still func-tioning, notably the Morro Velho mine, which is one of the deepest mines in the world. Today, the gold production of Brazil is insignificant when compared with world figures, but there are still many gold-bearing regions and it is probable that in at least some of them profitable returns would result from an exploitation program taking advantage of all the most modern innovations in gold mining and ore treatment on a large scale. In order to demonstrate the value of some of these abandoned pros-pects and stir up interest in increasing the national gold production, the government has stimulated research. Experimental plants have been and are being established in various places, and tests on large quantities of ores are being carried out on a semicommercial basis. The Geological Survey of the State of Minas Geraes is very active in this line and the Federal Institution is also showing an increased interest in the matter. One of the lesser known gold-bearing regions of Brazil is in the vicinity of Lavras, in the State of Rio Grande do Sul. Gold was first reported from this region in the early part of the nineteenth century. In 1811, D. João VI sent an experienced prospector from Minas Geraes to investi-gate the validity of the reports. According to the reports of Baron

Jan 1, 1934

By David E. Hyatt

The chemical attributes of cyanides have long been exploited in ore pro- cessing schemes for the recovery of copper, molybdenum, gold, silver, and other metal values. Blast furnacing operations are significant unintentional producers of cyanides which find their way into process waters. Many of the more than 20,000 electroplating facilities in the United States utilize cyanide plating baths and generate cyanide containing wastes. As social, political, and economic pressures for water quality attainment, maintenance, and preservation grow, the requirements for the development of treatment technology to control cyanide levels in wastewater become increasingly apparent. Just as the chemistry of the cyanide ion 1s an integral part of its industrial applicability, so must this chemistry be a fundamental part of any decomposition or removal technology used to control its level in effluent or recycled waters. The complexity of this chemistry is substantial and it cannot be considered in a superficial or cursory manner if control system design is to be both efficient and reliable.

Jan 1, 1975

By R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R' cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"'. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.' The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.' It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.'a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.' However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

Jan 1, 1966

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By AIME AIME

Award of a Gold Medal : to the Institute. The Jury of Awards of the Jamestown Ter-Centennial Exposition has conferred a gold medal, the highest distinction within its power,. on the American Institute of Mining Engineers for the excellence of its publications during the past decade. ; A half-tone photographic reproduction of both sides of the medal is given in the accompanying illustration.

Jan 7, 1908