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By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By M. B. Bever, A. B. Michael

THE structure of cast A1-Si alloys is altered profoundly by modifying agents. Sodium, in particular, reduces the size of the silicon particles in the eutectic and tends to change their shapes from plates to nearly rounded grains. This refinement is accompanied by a shift of the eutectic to higher silicon concentrations and lower temperatures. Similar effects can be attained by rapid solidification. Hypotheses advanced to explain modification have involved the formation of a ternary eutectic,1 the removal of oxides by fluxing,' and even a presumed allotropic transformation of silicon. Other hypotheses assume that the modifying agent causes an envelopment of the silicon particles by the aluminum-rich solid solution, but attribute this envelopment to different mechanisms. According to various explanations, the growth of the silicon particles is obstructed by an immiscible sodium-rich liquid," an adsorbed layer of sodium,' or a ternary compound;5 his obstruction has been conceived as purely mechanical or as a colloidal action.' It has also been proposed that sodium reduces the surface tension on the Al-Si interface, thus permitting the aluminum-rich solid to grow faster and to envelop the silicon particles.? Still other hypotheses stress undercooling and the attendant change in the rate of nucleation of silicon, but fail to ascribe any definite function to the sodium addition." '" Procedure High-purity alloys of aluminum and 3 or 7 pct Si were treated with modifying agents containing radioactive sodium tracers. The experiments were intended to investigate the partition of sodium between the primary aluminum-rich solution and the eutectic, and, if possible, to determine whether sodium is concentrated in or around the silicon particles in the eutectic. Radioactive sodium fluoride, alone or mixed with stable sodium chloride, was allowed to react with the alloy for 5 min immediately before solidification in the crucible. Modification could not be attained with additions of less than the equivalent of approximately 0.1 pct Na. Some alloys were not completely modified, but comparison of the structures of treated and untreated specimens indicated a very considerable reduction in particle size of the silicon in all of the former. A treated alloy is shown in Fig. 1. Radioactive sodium fluoride was prepared by bombardment with deuterons having an energy of 14 mev. This bombardment (totaling, for example, 6 microampere-hours in one run) produced radioactive Na24 (half-life 14.8 hr) by the reaction 11Na23 (d,p) 11Na24. The radioisotopes of fluorine also produced have short half-lives and were not detected. A half-life determination by counting confirmed that the measured activity was due to Na24. The distribution of the sodium in the solidified alloys was determined by an autoradiographic technique by which a suitable stripping film is attached to a very thin metallographic specimen. After exposure and development, this emulsion remains superimposed on the specimen and may be examined microscopically or photographed by reflected light. The emulsion of the autoradiograph can be correlated directly with the underlying surface by simple adjustment in focus. The details of this technique have been described elsewhere." Results Fig. 2 is a micrograph of the autoradiographic emulsion ("autoradiograph") lying directly above the area of eutectic in Fig. 1. Fig. 3 shows a similar autoradiograph of a region consisting of primary solid solution. The small black dots (tracks) in these autoradiographs are developed grains in the emul-

Jan 1, 1954

By W. C. Knopf, G. Samsel

For several years International Minerals & Chemical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large- scale plants. Natural potassium is composed of three isotopes -K39, K40 and K41. Five other isotopes, artificially produced, have been detected. In natural potassium only the K40 isotope, with a half life of 1.4 x 109 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes.

Jan 10, 1958

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.' The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.' Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900' to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,' when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By A. Vignes, J. P. Sabatier

A study of ternary diffusion at 1315°C in the Fe-Co-Ni system covering the entire ternary phase diagram has been carried out. Experimental values of the four interdiffusion coefficients DFeNico,DFeCoCo, DFeCoNi were computed at 33 points of the ternary diagram. The limiting values of these coefficients on the three sides of the ternary diizgram have also been determined. This set of data is presented as a contour map on the ternary isotherm for each of the four coefficients. Assuming that the Fe-Co-Ni system can be considered as ideal, the phenomenological coefficients Lk ij (with k = Fe) have been computed and the Onsager reciprocal relutions verified. It is shown that, in the Fe-Co-Ni system, the diffusion process can also be described by only two interdiffusion coefficients DFeFe and DCoNiFe, the second cross diffusion coefficient DCoFeNi being equal to zero and the second direct difusion coefficient being given by The values of the cross interdiffusion coefficients and of the Onsager coefficients are explained in terms of atomic mobilities of the three components with the help of a kinetic calculation due to Lane and Kirkaldy.8 It is shown that all the results are explained if the tracer difusion coefficients of the three components are such that DFe > DNi ~ DCo in complete agreement with experimental data on the three binary systems. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. In binary diffusion, there is just one independent composition variable and only one coefficient Dij is needed to describe the interdiffusion process. In ternary diffusion, we must allow for cross interaction between two independent species, and four interdiffusion coefficients are necessary to describe the transport process. Kirkaldy et al.1,2 have determined interdiffusion coefficients in the systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy4 have reported intrinsic diffusion coefficients for the r phase at 1300°C of Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.3 Interdiffusion coefficients were measured at three different compositions at 850°C in the single phase copper-rich corner of the Cu-Zn-Mn system by Dayananda and race.5 Zie-bold and Ogilvie6 have determined interdiffusion coefficients in the single-phase field of the Cu-Ag-Au system at 725°C. Preliminary results on diffusion at 1136°C in the system Fe-Co-Ni have been reported.7 In this study, data are reported on a more complete determination of interdiffusion coefficients in the Fe-Co-Ni system in the entire ternary at 1315°C. There is complete solid solubility with the fcc structures at 1315ºC, and this system can be considered as nearly ideal. This approximation allows the computation of the Onsager phenomenological coefficients. These values can then be used to test a kinetic calculation of the Onsager L coefficients in ternary substitutional solid solutions due to Lane and Kirkaldy.8

Jan 1, 1970

By Ralph J. Schilthis

Several investigators1-8 have reported evidence of the existence of native or connate water in oil-and-gas-bearing strata. Both water and salt have been detected in cores of oil sands that yielded oil and gas exclusively when produced. Electrical logs often reveal unexpectedly low resistivity through oil and gas sands, indicating the presence of some material that is a considerably better conductor of current than oil and gas. Furthermore, calculationsg of the oil and gas content of reservoirs based upon production and reservoir-pressure decline data indicate appreciably lower values than are arrived at under the assumption that the pore space is occupied completely by oil and gas. Origin and Occurrence of Connate Water in Oil-and-gas-bearing Formations The view has been expressed, 10-15 and is generally agreed upon, that the expulsion of oil and gas material from source beds and the subsequent migration and accumulation occurred in the presence of salt water. As the strata that usually form reservoirs for oil and gas were laid down by, or in the presence of, ancient seas, the pore space within the strata must have been saturated with salt water before the entrance of the oil and/or gas. Thus, the accumulation of oil and/or gas in the upper regions of structures suitable for reservoirs must have required displacement of the connate water therefrom. In the absence of any forces other than gravitational, it would be expected that the displacement of the connate water out of the zones finally occupied by gas and oil would be complete, and that the vertical distribution of gas, oil, and water in a reservoir would be strictly in the order of their densities. Apparently, however, surface and interfacial forces that will not permit complete segregation of the fluids are active within the capillary spaces comprising a reservoir. The effects of these forces on both accumulation and production of oil and gas have been the subject of study by a number of investigators.16-37 In general, the view is held that the character of most materials that make up the reservoir rock leads to preferential wetting of the rock by

Jan 1, 1938

By K. J. Anusavice, R. T. DeHoff, H. Oikawa, J. J. Pinajian

STUDIES of nickel self-diffusion and impurity diffusion in pure metals and alloys have, for the past two decades, employed predominantly the nickel radio-However, because of the low energy of the emitted particle, careful and time-consuming techniques must be used to obtain reproducible measurements. In our studies of nickel diffusion into copper, we have recently used Ni66 [Td1/2: 55 hr; : 0.20 Mev (100 pet)] which decays to it much more suitable as a tracer because of the presence of the high-energy y radiation from the cu66 daughter. Although the half-life of Ni66 is appreciably shorter than that of Ni63, the useful working lifetime of a small quantity, " 10 mc, is about 1 month. preparation bf Ni66. he Nis6 radioisotope was produced at Oak Ridge National Laboratory by means of a double (n,y) reaction:

Jan 1, 1969

By John C. Calhoun, Alfred Chatenever

An exploratory study wap made to examine the possibilities of a visual approach in investigations into microscopic mechanisms of fluid behavior in porous media. Appropriate apparatus and techniques were developed so that microscopic phenomena could be recorded on color movie film as well as be observed visually. The observation flow cells in which tlie fluid behavior studies were made were essentially single-layered matrices of spheres between plates. sometimes all-glass, sometimes all-Lucite and sometimes a combination of the two. The fluids were limited to water and a filtered crude oil. Two flow regimes were observed during the flow of the immiscible liquids: channel flow and slug flow. In the former, transport was effected through stable networks of interconnecting channels; and in the latter, part of the movement took place in the form of slugs. Under certain conditions, flood-front patterns were found to be different depending upon which liquids were the displacing and displaced phases and not depending upon whether the matrix was water-wet glass or oil-wet Lucite. Residual formations of oil and water were observed and are described. Some of the ramifications and significance of the ohservetl phenomena are discussed. INTRODUCTION In recent years considerations of microscopic mechanisms of fluid flow in porous media have taken on greater significance. Much needs to be learned before the fundamentals of petroleum technology are completely established. For example, many unanswered questions exist in connection with relative permeability, displacement phenomena, residua! fluid formations. flow structure, etc.; and further analytical mathematical formulations are seriously indicated. It is hoped that systematic investigations into the microscopic mechanisms connected with the behavior of fluids in porous media will shed some light on some of the problems extant. Until recently microscopic mechanisms have been considered almost exclusively as speculative hypotheses. Within the past few years, however, the problem has been submitted to a limited number of experimental investigations. Nuss and Whiting' made some studies on the pore-space geometry of sandstones and limestones by impregnating cores with an inert plastic and leaching the solid matrices to leave behind plastic models of the pore spaces. SchaeferZ traced pore spaces microscopically through lengths of limestone cores by cutting away thin sections from the exposed faces normal to the line of view. In 1949 two projects were organized in which dynamic flow phenomena were examined microscopically to uncover microscopic mechanisms. One was set up at the Pennsylvania State College where Lowmanb bserved heterogeneous fluid flow phenomena in capillaries. The second was the American Petroleum Institute Research Project 47B at the University of Oklahoma where microscopic studies of dynamic fluid phenomena in synthetic porous matrices have been made by visual observation and cinephotomicrography.' It is with the latter that this paper is concerned. treating the techniques involved and the observations made. TECHNIQUES Observation Flow Cells The observation flow cells formed a focal point in the techniques employed. Essentially, these were matrices composed of a single layer of spheres sandwiched between two flat plates. This design was arrived at after a series of pre-

Jan 1, 1952

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By H. E. Nold

High-volatile coals are most desirable for kiln firing. Low-volatile and even anthracite coals can be used successfully. Most periodic kilns use coal and are hand fired. A few stoker installations have been economically successful. Continuous tunnel kilns reduce fuel consumption 40 to 55 per cent. They are rapidly replacing periodic kilns in the manufacture of the finer wares. They have found great favor in the refractory industry and are successfully used in firing almost all kinds of heavy clay products. Fuel oil has found rather wide application in the Southwest and West. Natural gas is a satisfactory fuel for kiln firing. It is the principal competitor of coal and has largely replaced it for firing the finer wares but cannot compete with it in firing heavy clay products except in regions where cheap gas is available. Figures are given showing the relative thermal efficiency of coal and natural gas as used for firing ceramic ware. The ceramic industry uses from 12,000,000 to 12,500,-000 tons of coal per normal year. The principal use of coal is in firing the heavy clay products. This potential market amounts to about 9,250,000 tons per year. Coal producers could increase sales by furnishing expert firing instruction.

Jan 1, 1934

By Byron W. Cheever

In working up the process which I described at the Chicago Meeting, May, 1884 (p. 163 of the present volume), for the estimation of phosphorus in iron and steel, I employed samples of steel obtained from one works only, and of a given brand. Since then I have had frequent occasion to test the process on other steels, and find that it works equally well. But some steels present certain colors which may mislead the operator; and I therefore propose a slight change in the directions formerly given. On the second page of my paper, in the second paragraph, I would substitute the following modified directions: Place the flask under the hydrant, till the solution is perfectly cold ; then add, gradually, strong ammonia, with constant stirring, till the solution is changed into a pasty mass and the ammonia is in slight excess; then add cautiously HNO3 (1.40 specific gravity)

Jan 1, 1885

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.' When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By Arthur C. Spencer

Having suggested magmatic waters as the probable agents of vein- and ore-deposition in Southeastern Alaska in a paper entitled, The Geology of the Treadwell Ore-Deposits,' it is with particular interest that I note Mr. W. Lindgren's application of the hypothesis of igneous emanations to the gold-quartz veins of Victoria and of California. After describing the similarities of the veins and of the changes in the wall-rock due to the action of vein-waters in the two regions considered by him, Mr. Lindgren formulates the hypothesie that the veins of this type " have been deposited chiefly by ' eruptive after-effects ;' in other words, chiefly by hot ascending waters originally contained in the granitic magma and relased from it by decreasing pressure, due to its irruption into the upper parts of the litho-sphere. It is quite possible that atmospheric waters may have played a certain part by aiding the precipitation and by effecting certain forms of concentration in the deposits." There are many reasons for extending this hypothesis to southeastern Alaska. This region and the Sierra Nevada belt of California are undoubtedly parts of one geologic province, throughout which the main events of geologic time are evidenced by identical or closely similar records in the rocks. Our knowledge of the former region is still fragmentary, to be sure; but the origin-dates of the most prominent features of geology have been located in the time-scale, and found to correspond completely with the red-letter dates in the Californian record. In both there are: (1) intense folding and meta-

Jan 1, 1906

By W. R. Wardner

During 1928 low prices in the East greatly restricted the Atlantic market for California petroleum. The situation was made difficult by only partial control of production. The month of December is estimated in the figures presented here and it is hoped that the differences in the final figures will be immaterial. Daily averages are used throughout. Production Daily average crude production for 1928 was 633,942 bbl., very little more than 1927. Natural gasoline production was 35,453 bbl. daily and the supply (crude and natural gasoline) was 669,395 bbl. However, potential supply was 785,621 bbl. daily, 47,436 more than that of 1927. This is accounted for by more production being shut in so that 116,000 bbl. daily was conserved in 1928 which would otherwise have been produced. Fig. 1 shows production by months for 1928. It will be noticed that while crude production held fairly uniform from January to October, the

Jan 1, 1929

By AIME

Compiled by Mary Ann Gross, Department of Energy. Bruceton. PA. Supplemental data from Coal Age indicated by (*). Reprinted by permission from CoalAge magazine.

Jan 1, 1981

By William H. Spice

No devclopment of major importance has been made in the south central fault-line district of Texas during 1939. Four new fields have been discovcred, all of which appear to be of minor importance, with small wells in the Navarro sand, the Taylor marl or the Austin chalk. Drilling along the fault line has not developed any new prospects in the Edwards lime, the most prolific producing horizon of the district. At the close of the year, a few deep tests for lower producing horizons have been projected and should prove to be of interest, and plans are under way for further development of the Pearsall field, which has been under the control of a single company until recently. Production from the 46 producing fields was maintained at 8,460,000 bbl. for the year, a decrease of approximately 400,000 bbl. under 1938. This decrease is due in part to natural decline of production and in part to decreased allowed production. Approximately 55 producing wells were completed on proven acreage in the Darst Creek and Salt Flat fields. No new lease plays were made during the year, although approximately the same amount of land, 600,000 acres, remained under lease during the year. Some geophysical operations of various types were carried on along the fault-line area itself and also in the Edwards plateau and in the area south and southeast of the main fault line.

Jan 1, 1940

By William H. Spice

No devclopment of major importance has been made in the south central fault-line district of Texas during 1939. Four new fields have been discovcred, all of which appear to be of minor importance, with small wells in the Navarro sand, the Taylor marl or the Austin chalk. Drilling along the fault line has not developed any new prospects in the Edwards lime, the most prolific producing horizon of the district. At the close of the year, a few deep tests for lower producing horizons have been projected and should prove to be of interest, and plans are under way for further development of the Pearsall field, which has been under the control of a single company until recently. Production from the 46 producing fields was maintained at 8,460,000 bbl. for the year, a decrease of approximately 400,000 bbl. under 1938. This decrease is due in part to natural decline of production and in part to decreased allowed production. Approximately 55 producing wells were completed on proven acreage in the Darst Creek and Salt Flat fields. No new lease plays were made during the year, although approximately the same amount of land, 600,000 acres, remained under lease during the year. Some geophysical operations of various types were carried on along the fault-line area itself and also in the Edwards plateau and in the area south and southeast of the main fault line.

Jan 1, 1940

By R. E. Gilchrist, R. R. Harvey, M. R. Dean

A simple and rapid three-component analysis procedure has been developed for use in fluid-flow studies. The method is based on refractive index measurements, combined with refractive dispersion measured between the Ha and H wave lengths. The procedure requires. calibration curves for the three-fluid system. The only restriction on the fluids employed is that only one be an aromatzc or olefinic compound. Individual sample measurements require only a few minutes. Composition results within the limits of accuracy required for fluid-flow analog studies are obtained. INTRODUCTION The simultaneous analysis of three-component mixtures is a problem often encountered in fluid-flow analog systems. In petroleum production research, the problem is usually encountered in experiments on the displacement of fluid from a porous medium. In the case of immiscible displacement, simple volumetric measurements of the produced fluids are usually sufficient, the analog fluids often being the actual reservoir fluids themselves — oil, water and gas. However, modern secondary recovery of petroleum sometimes involves production under miscible conditions, in which the oil is displaced by liquefied petroleum gas which, in turn, is displaced by dry gas. Since this type of displacement is done under conditions of pressure and temperature that are not easily reproduced in the laboratory, studies are often performed with analog fluids at essentially atmospheric pressure. Since the number of samples taken during one of these experiments is usually quite large, the time required for analysis becomes an important factor. In the past, the difficulty of conventional analysis has been avoided by the addition of various tracers to one or more of the components, or by the use of a tracer fluid as one of the components. With these techniques, a relatively large amount of analytical time is still required. Moreover, in the case of added tracers, the tracer material may migrate in part to one of the other fluids, may be adsorbed on the solid surfaces of the model, or may introduce side effects not characteristic of the prototype fluid. The substitution of a tracer fluid for one of the components can severely limit the choice of analog fluids. Optical refractometry provides a rapid and economical method of analysis of two-fluid systems or of monitoring small changes in composition of an essentially one-component system. Refractometric methods are capable of high degrees of accuracy, require only very small samples and can easily be adapted to automatic methods. They are not generally applicable, however, where three or more fluids are present over wide ranges of concentration. The method of three-component analysis described here has three essential characteristics. 1. It is based on refractometric measurements and thus preserves all of these desirable properties. 2. It does not make any stringent demands on the choice of fluids that can be analyzed. 3. It is capable of accuracy sufficient for fluid-flow analog studies. THEORETICAL The difference in the refractive index of a substance at two different wave lengths of light is known as its dispersivity. When the difference is taken between the specific refractions at the two wave lengths, the quantity is referred to as the specific dispersivity. Specific refraction was defined empirically by Gladstone and Dale1 as r = n-1/d....[1] where n is the index of refraction and d is the density. The definition is given more correctly by the expression r =n2-1/n2+1 1/d..........(2) 1References given at end of paper. MICIFTV OF PETROLEUM ENGINEER JOURNAL.

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear to divide into two or more branches within a short distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down com¬mences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat-marsh moving on in that direction, the other side may be rising,

Jan 1, 1873