Search Documents

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By P. H. Thornton

MaNY intermediate phases are solid solutions which have a solute-solubility range greater than 3 at. pct. These phases, which are generally very strong and often have simple crystal structures, are usually extremely brittle so that specimens of simple shape cannot be produced by the usual mechanical-deformation techniques. Furthermore, single crystals of reasonably uniform composition are difficult to grow by the Bridgman technique because the phases generally form by a peritectic reaction, which causes pronounced segregation. In this note, a technique is described for the preparation of thin-rod specimens of brittle intermediate phases, which may be used for physical-property studies such as resistivity changes' and for the conversion of such rods into single crystals. The method has been used for the preparation of rod single crystals of the phases and Ingots, of about 100 g weight and 11 mm diam, were made by melting together the appropriate amounts of high-purity materials (usually 99.999 pct) in sealed

Jan 1, 1967

By I. L. Dillamore

I. L. Dillamore (University of Birmingham)—The different textures developed in various fcc metals have long awaited satisfactory explanation and it has now become clear that these differences are related to parallel differences in the deformation characteristics of the metals. Liu is correct, therefore, in seeking to account for the observed textures in terms of the flow mechanisms but I believe, for the reasons outlined below, that the particular interpretation of flow mechanisms proposed by Liu is open to substantial objections. By considering the forty-eight possible designations of the twelve octahedral slip systems found in fcc metals as distinct and separate deformation modes, Liu has fallen into the error of assuming that only positive glide dislocations associated with each system are present. In fact both positive and negative dislocations will be present and the only difference between for instance the systems B4 and B4' (in Liu's notation) is that under a stress of given sign the direction of motion of a dislocation is reversed on changing from B4 to B4'. For both orientations positive and negative dislocations will be present. In considering possible dislocation interactions it is, therefore, inadmissible to differentiate between R4 and R4' as Liu does. Liu considers those dislocation interactions which give the biggest reduction in energy to be the most favorable and neglects, on the grounds that they will form strong barriers to slip, interactions between dislocations with perpendicular Burgers vectors. Setting aside interactions between positive and negative dislocations of the same slip system, which must occur regardless of the combination of slip systems chosen, the biggest reduction in energy occurs for the Lomer-Cottrell interaction and it is Lomer-Cottrell barriers which are thought to provide the stronger dislocation obstacles. On the other hand the intersection of dislocations with perpendicular Burgers vectors is thought to be a low-energy process which contributes only a fairly small temperature-dependent part of the total work hardening. On this basis it seems doubtful whether the reduction in energy through possible dislocation interactions provides a reasonable criterion for choosing the operative slip systems. From the point of view of texture development it is unsatisfactory to ignore the slip rotations leading to an end position and to neglect to consider the stability of the chosen end point. It is also unsatisfactory to treat the two stress axes as interchangeable since, if the stress system is idealized as biaxial, one stress is compressive and the other is tensile. For the same reason the rotations of the two stress axes are not made compatible simply by assuming that the same slip directions are responsible for the rotations of the two stress axes. It is, in short, essential to treat the two stress axes as acting together on the same slip systems. Turning to the question of the difference between the copper-type and the brass-type texture, there now remains little doubt that the difference is attributable to differences in stacking-fault energy (y), as noted by Liu, but it is doubtful whether the temperature dependence of the texture in copper and in silver is due to increasing stacking-fault energy with increasing temperature. The results of Swann and Nutting42 cited by Liu were obtained in Cu-A1 alloys and the apparent increase in stacking-fault energy on raising the temperature may be influenced by short-range ordering. In pure metals such effects are absent and the only data available on the variation of y with temperature are those of Buhler et a1.43 for silver. They report a minimum at 200°C which does not fit the hypothesis put forward by Liu. It is much more likely that thermal activation of cross slip is important in determining which texture develops, as proposed by Dillamore and tors. These workers have proposed an explanation for the differences in observed texture among the fcc metals and the pole figures predicted consist of an orientation spread which is in better agreement with observation than the limited number of discrete orientations suggested by Liu. The theory of Dillamore and Roberts is also able to account for the differences between aluminum and copper which Liu still leaves unexplained. Y. C. Liu (author's veply)—The writer appreciates the interest of Dr. Dillamore, but must discuss some of his comments in order to avoid cross purposes. The phrase, "forty-eight slip systems," which appeared twice in the text—in the caption of Fig. 1 and the first paragraph in the Discussion—might unfortunately have led Dr. Dillamore to disagree

Jan 1, 1965

By B. L. Landrum, P. B. Crawford

The rise of a new laboratory model for studying tran-sient fluid flow problems, is described. The theory of he model is based on the analogy between the equa-ions which describe the flow of compressible fluids in porous media and the conduction of heal m solids. The "thermal model" is used to study the Iransient Pressure distributions during fluid displacement in five Standard well patterns. The studies indicate quantita-ively how die pressures change with lane at any poit in the reservoir. It was found that, in general, the equipressure contours are more radial about the wells early in the program than after steady-state conditions are established. In addition two studies of fractured five-spot patterns are presented to illustrate the opplicability of the model for a wide range of reservoir conditions. INTRODUCTION In reviewing the oil recovery techniques involving fluid displacement it was found that a very considerable quantity, if not all of the fluid within the pattern, mav be displaced (during a time-dependent or transient period rather than the usually applied steady-state conditions. Since the oil is displaced during a transient period, it was believed desirable to study the nature of the transients for several of the commonly used fluid displacement patterns. A literature review indicated fairly complete studies of the streamlines and isopotentials for steady-state: yet few data were available on the transient displacement process. Several simulated steady-state multiwell displacement programs were carefully mapped by Foster and Lodge on an electrical conducting sheet as early as 1875, hut the more recent work of Muskat provides the best source for steady-state phenomena having direct petroleum production applications. In order to study the transient phenomena a new lab-oratory model was developed which is based on the similarity of the equations that describe the flow of fluids and the conduction of heal. The equations describing heat flow were developed early in the nineteenth century. Regorous solutions tor most transient problems are in gcneral complex and usually limited to fairly restricted houndary conditions.2 the thermal model may be used to obtain approximate solutions for many transient problems without some of the restrictions required for analytical solution. The application of the analogy between heat conduc-. tion in solids. electrical flow and fluid flow, in a porous media has long been recognised. Techniques originally developed for the solution of heat conduction prol?lems have in many instances proved useful in ohtaining solutions to fluid flow prohlcms. Ir is not surpri5ing then that a heat conduction or thermal model might bf usefull in sludying transient fluid flow. As an example ol the problems suitable for the study with the thermal model, transient pressure distributions during fluid displacement programs are studied for the five-spot, line-drive, staggered line-diibe. seven-spot 211 two fractured patterns. A model was constructed of an iron plate of geometry similar to the reservoir patterns under study. The principle of mirror images as suggested by Bryan was employed in shaping the model. A temperature differential was obtained by soldering two sections of copper tubing to the plate at points analogous to the well location in the field. Hot and cold water was passed through the tubing. The temperature distribution, analogous to the pressure distribution in the field. was obtained a a function of time from thermocouplcs distributed over the plate.

By D. R. George

Preliminary research has identified several organic and aqueous solutions that are effective absorbents for SO, from simulated smelter gas containing 0.3 to 2% SO2. These SO2 loaded solutions are also compatible to the reaction of H2S and SO2 to precipitate a readily filtered elemental sulfur. The economic removal of SO2 and production of elemental sulfur from stack gases discharged by base- metal smelters is a challenging goal. The magnitude of this task is illustrated by the estimate that about 3.5 million tons of SO2 are discharged to the atmosphere by smelters annually in the U.S. The SO2 concentration of the gases ranges from about 0.5 to more than 3%. As the sulfur content of SO2 is 50% a potential production of 1,750,000 tons of sulfur per year is indicated.

Jan 1, 1970

By I. E. Rosenzweig

THE problem considered in this paper is as follows: An arbitrary horizontally stratified area is given. The electrical properties of this area are characterized by a function p(z) (Fig. 1), which shows the relationship between resistivity p of thes oil and the depth z. For such general case the apparent resistivity p* will be computed, by FIG. 1.-GRAPH OF FUNCTION p(z) FIG. 2.-GRAPH OF p(Z) FOR n HOMO-GENEOUS LAYERS. earth-resistivity measurements carried out by any given configuration of electrodes. General solutions of this problem appear to be very important for interpretation of field results of resistivity measurements, concerning structural investigations. Such solutions have been given by many authors for the special case of a finite number of homogeneous layers (Fig. 2)1-4 as well as for the more general case of continuously rang-ing resistivities. 5-8

Jan 1, 1939

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By John R. Weeks, Dan McLachlan, John R. Lewis

DURING the operation of the iron blast furnace, aggregates of hard, infusible, yellow, cubic crystals frequently form in the interstices of the lining and on the hearth of the furnace. These were first examined by Wohler&apos; and were identified by him as a complex cyanonitride of titanium, having a formula Ti(CN)2 • 3Ti3N2, or more simply Ti10C2N8. However, recent investigators have suggested that this complex compound does not exist. Recent work by Hume-Rothery, Raynor, and Little2 on the carbide and nitride particles in titanium steels suggests that a complete series of solid solutions of the general type Ti<0+y>C0Ny exists between titanium carbide (Tic) and titanium nitride (TiN). Assuming this to be true, it seems likely that Wohler&apos;s cyanonitride of titanium is in reality a solid solution of 20 mol pct Tic in 80 mol pct TiN, .the nearly consistent carbide-to-nitride ratio probably resulting from temperature and pressure conditions in the blast furnace. The object of the present work was to investigate thoroughly this possibility of a solid solution by using the single-crystal methods of X-ray analysis. A spectrographic qualitative analysis of a sample of the yellow crystals furnished by the Geneva Steel Co. sh&apos;owed, in addition to the titanium, strong lines of vanadium and moderate to weak lines of iron, magnesium, silicon, aluminum, and calcium. The last five were probably slag impurities, but the vanadium was possibly included in the yellow crystals, owing to a great structural similarity of its carbide (VC) and its nitride (VN) to the titanium compounds, Table 11. A chemical analysis was made

Jan 1, 1952

J. L. JONES,* Pittsburgh, Pa.-If a nickel anode is cast under commer-cial conditions, will it contain nickel oxide? Will the nickel oxide affect the rate of corrosion in a double sulfate solution; or will the nickel oxide dissolve in a double sulfate solution? I would also like to ask whether a 98 per cent. pure nickel anode will corrode as fast as a 96 per cent. nickel anode; whether electrolytic nickel will corrode less rapidly than nickel containing a small amount of carbon; and whether the materials some-times used in coating molds for casting nickel anodes will affect the rate of corrosion of the anode? In other words, whether an electrically non conducting coating is likely to be present that will prevent the nickel anode from corroding rapidly. JOHN F. THOMPSON.-The nickel oxide will not dissolve in the double sulfate solution, as far as we know. We do not make the ordinary nickel anode of commerce, but we supply nickel to the nickel anode makers. Those makers almost invariably buy a high-carbon nickel shot, ranging around 0.45 per cent. carbon. In their process, they even further, car-burize it so as to get nickel that will melt easily and be fluid enough to fill the mold, so that the ordinary cast anode on the market is unquestion-ably oxide free. The only time that such an anode will have oxide will be through an error in melting. Some cupola makers of anodes have had trouble with oxidation, but as a rule the anodes are thoroughly carburized; so much so that they probably carry a couple of per cent. of carbon of which around. 1.6 per cent. is graphite.

Jan 12, 1919

By D. W. Fuerstenau

Measurement of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions. Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus. The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes.

Aug 1, 1956

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG&apos; and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&&apos; and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-&apos; as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.&apos; and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott&apos;s "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

Joseph W. RichaRds, South Bethlehem, Pa. (communication to the Secretary*): The hold experiment of Mr. James Gayley in drying the blast used in the Isabella furnace has attracted the attention of the whole metallurgical world, and has given rise to a wide discussion of the reasons for its great success. Mr. Gayley and the capitalists who backed him in his work deserve congratulations on the success of the venture, not only because it succeeded, but because they have been rewarded far beyond the maximum that could be expected from theory or probability. To state the case in its simplest terms, all that could have been predicted was: (1) that the removal of the moisture from the blaet would result in the saving of the heat required for its decomposition, representing from 3 to 5 per cent. of the heat-value of the coke used; hence about that quantity of fuel might be saved; (2) that the furnace would be somewhat more independent of variations in the weather; (3) that the campaign would be a little hotter; and (4) that the speed of the blowing-eugines would be decreased, at least in amount proportionate to the reduction in temperature of the air led to them. I do not think anyone anticipated a much larger output per day. The results actually attained were: (1) the furnace made an increase of 24.86 per cent. in the output of pig-iron per day; (2) it consumed 19.6 per cent. less coke per ton of pig-iron made; (3) the blowing-engines were run 15.8 per cent. slower; and (4) the saving in power made up for the power required to run the refrigerating-plant. In addition, the blast was hotter; the waste-gases cooler, because of their smaller volume; and there was a greater proportion of carbon dioxide to carbon

Jan 1, 1906

By C. D. Stahl, S. M. Farouq Ali, W. E. Culham

One- and two-dimensional mathematical models have been developed that simulate transient, two-phase flow of hydrocarbon mixtures in porous media in a manner that accounts for interphase mass transfer. Numerical simulations of one-dimensional depletion-drive experiments using a two-component hydrucarbon fluid were used to establish the validity of the mathematical models. In addition, the experimental and numerical data were used to demonstrate that production rate had a relatively insignificant effect on the recovery of individual hydrocarbon components from the experimental system, and that attainment of equilibrium between phases is possible for a wide range of liquid and vapor velocities in reservoirs containing light hydrocarbon fluids. Results of some two-dimensional numerical simulations are also presented. INTRODUCTION This study was undertaken to develop a mathematical model that would simulate transient, two-phase flow of hydrocarbon mixtures in porous media under conditions that result in interphase mass transfer and to test the validity of the assumptions used to set up the model. In addition, the study was designed to determine if production rate influences the recovery of individual hydrocarbon components from reservoirs producing by depletion drive. Two-phase flow in porous media, with interchange of components between the two phases, is important in many petroleum recovery processes. Studiesl-5 conducted within the last 3 years have outlined methods of solving multiphase flow problems incorporating mass transfer. Some of these studies have also indicated the importance of accounting for mass transfer under various producing conditions. An earlier work6 first demonstrated the importance of combining relative permeability data with equilibrium ratios in compositional balance methods. The mathematical model presented in this paper is formulated so that a phase behavior package, as described in previous papers,5,17 is not required as an integral part of the routine employed to solve for the primary dependent variables. The finite difference formulation is designed so that all the primary variables can be solved for simultaneously. This is accomplished by utilizing one basic set of equations. These innovations, which are in contrast to other models2,3,5 but are similar in some respects to the approach used by Taylor,l render the total problem computationally simpler than any of the previously referenced formulations. The mathematical model was developed by combining Darcy&apos;s law with a continuity equation for each hydrocarbon component. The principal assumptions invoked in the formulation were (1) that capillary forces and diffusional effects are negligible, and (2) that thermodynamic equilibrium exists in the reservoir at all times. No assumption as to the type of vaporization process was made in formulating this model. Experimental data were required to complete this study. These were generated by conducting several depletion drive experiments. The experimental apparatus consisted of a sandstone core enclosed in a pressurized casing. The apparatus was designed in such a manner that the core could be charged with a liquid hydrocarbon mixture and depleted at different production rates. The experimental tests were designed to determine the effect of production rate on component recovery. In addition, direct comparison of experimental and mathematically predicted

Jan 1, 1970

By A. J. Lena, M. F. Hawkes

Changes in hardness, tensile properties, microstructure, electrical resistance, and X-ray diffraction effects indicate that lattice strains are necessary for the embrittlement of ferritic stainless steels when heated for relatively short times at 475°C (885°F). It is suggested that 475°C (885°F) embrittlement is due to the accelerated formation of an intermediate stage in the formation of s under the influence of these strains. FERRITIC stainless steels (low carbon alloys of iron with more than 15 pct Cr) are subject to two forms of embrittlement when heated in the temperature range of 375° to 750°C. The embrittlement which occurs after long time heating between 565" and 750°C is well understood; it is caused by the precipitation of the hard, brittle s phase. Sigma is an intermetallic compound of approximate equi-atomic composition with an extended range of formation in Fe-Cr alloys. The maximum temperature at which this form of embrittlement can occur is dependent upon chromium content; and is approximately 620°C for a 17 pct Cr steel and 730°C for a 27 pct Cr steel. The other form of embrittlement occurs after relatively short heating periods in the range of 375" to 565°C; in the higher chromium steels, hours may be sufficient as compared to months for s embrittlement. This phenomenon is not at all well understood and several controversial theories have been proposed. The rate and intensity of embrittlement increase with increasing chromium content but the maximum rate occurs at 475°C re-gardless of chromium content. As a result of this, the phenomenon has been termed 475°C (885°F) embrittlement. The effect of 475°C embrittlement on the properties of ferritic stainless steels has been thoroughly reviewed by Heger.1 The embrittlement causes a pronounced decrease in room temperature impact strength and ductility, a large increase in hardness and tensile strength, and a decrease in electrical resistivity and corrosion resistance. Microstructural changes accompanying embrittlement are minor and difficult to interpret with a general grain darkening, appearance of a lamellar precipitate, grain boundary widening, and precipitation along ferrite veins having been reported at various times. With the exception of reported line broadening, X-ray diffraction studies by conventional Debye analysis of solid samples have been of little value. BY making use of electron diffraction methods, Fisher, Dulis, and Car-roll&apos; have recently shown the existence of a chromi-um-rich, body-centered cubic phase in 27 pct Cr steels which had been aged at 482°C (900°F) for as long as four years. Two types of theories have been advanced to account for the embrittlement. The first of these requires the precipitation of a phase not inherent in the Fe-Cr system with various investigators suggesting a carbide,3 nitride,3 phosphide,4 or oxide." Theories of this type have difficulty accounting for the influence of alloying elements on the embrittlement and for the facts that a minimum chromium content is necessary for embrittlement and the intensity of embrittlement increases with increasing chromium content. The second type of theory that has been proposed relates 475°C embrittlement to s phase formation which is inherent in the Fe-Cr system. An assumption of this kind can adequately explain the influence of alloying elements, for they exert an effect on 475°C embrittlement similar to that on s phase for-mation as can be seen in Table I. The minimum chromium content is essentially the same for both phenomena and it has been shown12,13 that s is a stable phase in the embrittling temperature range. In addition, it has been reported14,15 that pure alloys embrittle to the same extent as commercial type alloys. There are, however, several factors which have prevented complete acceptance of a s phase theory. Foremost of these is that the embrittlement can be removed by reheating for short time periods above 600°C, which in the higher chromium steels is within the stable s region. No s has ever been observed after one of these curing treatments, nor has any s been found as a result of embrittlement at 475°C. In addition, the simple precipitation of s cannot explain the time-temperature relationships for reactions between 350°and 750°C. This behavior is shown schematically in Fig. 1. Newell 16 and Ried-rich and Loib4 have shown that 475°C embrittlement follows a C-type curve as illustrated, while Short-

Jan 1, 1955

By Stanley J. LeFond

Brazil is one of the most outstanding examples of economic development of our time. Its amazing growth record is substantiated by a GNP which has increased at an average rate of 92% for the period 1968-1970 and estimates for 1971 range from 11.7-12.5%. Hence, this growth, coupled with a more relaxed attitude of the Brazilian government towards foreign participation in business opportunities and the remittance of profits out of the country, has caused many exploration companies to reevaluate the potential of Brazil. Despite recent press notices and publicity, Brazil is still not a mining country in the tradition of Canada or Australia. It is still basically an agriculture and manufacturing country.

Jan 11, 1973

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By William Klement

KNELLER&apos; has recently reported that extensive metastable solid solutions may be obtained in Cu-Fe alloys by simultaneous vapor deposition. This note reports that solid solutions, apparently single -phase, can be obtained for Cu-Fe alloys containing 0 to 20 and 85 to 100 at. pct Fe by rapid quenching from the melt; the inability to extend the solid solubilities further is related to the liquid miscibility gap, Fig. 1, as for Cu-Co alloys.2&apos;3 Accurate lattice spacings of the copper-rich fcc and iron-rich bcc solid solutions have been obtained. Homogeneous alloys were prepared by casting4&apos;5 and sintering2 from elements of 99.9+ pct purity. The quenching techniques were as before,&apos; except the iron-rich alloys were liberally covered with argon while at elevated temperatures. Flakes about 1 sq mm in area were obtained and investigated with the Debye-Scherrer technique, as previously described.2,4 All X-ray work was done at 25° 2°C using filtered copper and cobalt K radiation. Relative visual intensities of the diffraction lines for the phases in the quenched alloys are shown in Table I. The lattice spacings of the fcc structure for alloys containing up to 80 at. pct Fe are plotted in Fig. 2. The variation of these lattice parameters with composition is in good agreement with the re- of cementite spots usually present (all hkl reflections are allowed) and the ease of confusing them with ferrite or martensite reflections. Copies of the report can be obtained by writing to the Materials Research Department, Rocketdyne. 6633 Canoga Avenue, Canoga Park, Calif., 91304. A copy is also available at the Engineering Societies Library, 2nd floor, 345 East 47th Street, New York, N.Y., 10017. Photocopies, either full-size or microfilm, may be purchased from the Engineering Societies Library. sults6 of Andersen and Kingsbury, Fig. 2, although there is some disagreement in absolute value. This discrepancy may be due to the different temperatures at which the X-ray measurements were carried out and perhaps to the different extrapolation procedures. Also, Andersen and Kingsbury6 state that their lattice spacings were computed relative to the wavelengths given by Siegbahn in 1933; this reference has not been found and it is assumed that the well-known 1931 wavelengths were used, the lattice spacings then being in kx units which are converted into angstroms by the factor 1.00202. There is no support for the contention that solution of iron decreases the lattice parameter of copper, as con-

Jan 1, 1965

By Arthur R. Still, Paul Gilmour

The ore deposit of the Iron King mine occurs in a group of steeply-dipping metamorphosed eugeosynclinal volcanic and sedimentary rocks of Precambrian age. Within this sequence, the ore deposit lies at the contact of a unit made up of rhyolitic tuff and interbedded andesite and a structurally underlying series consisting of andesitic tuffs, minor rhyolitic tuffs, and argillaceous sediments. Field evidence suggests that these rocks have been overturned. The ore deposit is made up of a series of overlapping, conformable or bodies consisting of massive pyrite and associated lenses of massive quartz. These contain recoverable amounts of gold, silver, lead, zinc, and copper. A parallel zone of copper mineralization occurs within the hanging-wall rocks. The deposit is considered to belong to a large and important group characterized by mineralogical composition and the lithology and structural type of the host rocks. Evidence regarding the origin of the deposit is reviewed, and it is concluded that the ore bodies were formed through the agency of volcanic hot springs on, or near, a submarine surface of deposition

Jan 1, 1968

By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever&apos;s4 work on iron. Barnett&apos;s7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965