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By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By B. D. Cullity

A distribution of residual stress after plastic elongation is proposed, in which the bulk of the material is strained in compression and a very small portion in tension, This distribution is shown to account both for the X-ray observations and for the effect of plastic straining on magnetic losses in silicon steel. The regions left in compression are tentatively identified with the interiors of the sub-grains revealed by the electron microscope. THIS paper is concerned with the general problem of the nature of the residual stress which is produced in metals by plastic elongation. A particular stress distribution will be suggested which accounts for the main X-ray diffraction observations which have been made. It will also be shown that certain magnetic measurements made on silicon steel can be understood in terms of this stress distribution. X-RAY OBSERVATIONS Uniform straining of a crystal lattice (macro-strain) causes a diffracted X-ray beam to shift its position, and nonuniform straining (microstrain) causes line broadening. If a bar of metal is plastically elongated in the longitudinal x direction and then unloaded, diffracted X-ray lines are observed to be both shifted and broadened.'-= Although the observed line shift indicates the presence of macro-strain, experiments have shown that no macrostrain, in the usual engineering sense of the term, exists.5"7 For example, removal of a layer from one surface of a stretched and unloaded bar does not produce curvature in the remainder of the bar 5'7 Fig. 1 shows the variation of lattice strain in the x direction, as determined from X-ray line shifts, with the applied stress in the same direction. The curve ABC is the normal stress-strain curve of the material, AB being the elastic portion and BC the plastic. In the elastic region AB, the strain measured by X-rays, called the lattice strain, and the strain measured mechanically are both proportional to the applied stress, and both return to zero when the applied stress is removed. Above the elastic limit the lattice strain would be expected to continue to increase along the line BD. Actually, it increases less rapidly with respect to stress, or even decreases, as shown by BE. If the applied stress is then decreased, the lattice strain decreases along EF, which is parallel to AB. As a result, there is a compressive residual lattice strain FA after unloading. STRESS DISTRIBUTION. Since a stretched and unloaded bar does not contain macrostress, it follows that the observed line shift must be due to a special distribution of mi-crostress. Such a distribution is shown in Fig. 2, which shows the variation of the stress u, across a stretched and unloaded bar. The material is assumed to consist of two kinds of regions: regions C, stressed more or less uniformly in compression, comprising the bulk of the volume of the material and responsible for the observed diffrac-

Jan 1, 1963

By A. Werenfels

After discussing the geology of the Limagne, the surface indications of petroleum, and the recent exploration, the author states that none of the wells were properly located and that oil possibilities of the Limagne have not been adequately tested. NO PETROLEUM, in commercial quantities, is found in France except the small production of the Pechelbronn field (Fig. 1) in Alsace, which produced 75,000 tons in 1923; therefore the test of the petroleum FIG. 1.-KEY MAP. prospects of the Limagne is most interesting. Under the superintendence of M. Termier, chief engineer of the French mines, a well near Crouelle (Fig. 2) was drilled in 1921 to a depth of 856.3 m. (2808 ft.); at different depths favorable showings were encountered. The well, however, was abandoned because of drilling difficulties. A second one is now being drilled near the same place.

Jan 12, 1924

By J. Handin, S. J. Bauer, M. Friedman

Deformation mechanisms in room-dry and water-saturated specimens of Charcoal Granodiorite, shortened at 10-4s-1, at effective pressures (Pe) to 100 MPa and temperatures to partial melting (?1050°C) are documented with a view toward providing criteria to recognize and characterize the deformation for geological and engineering applications. Above 800°C strength decreases dramatically at effective pressures ? 50 MPa and water-weakening reduces strength an additional 30 to 40% at Pe = 100 MPa. Strains at failure are only 0.1 to 2.2 percent with macroscopic ductility (within this range) increasing as the effective pressures are increased and in wet versus dry tests. Shattering (multiple faulting) gives way to faulting along a single zone to failure without macroscopic faulting as ductility increases. Microscopically, cataclasis (extension microfracturing and thermal cracking with rigid-body motions) predominates at all conditions. Dislocation gliding contributes little to the strain. Precursive extension microfractures coalesce to produce the throughgoing faults with gouge zones exhibiting possible Riedel shears. Incipient melting, particularly in wet tests, produces a distinctive texture along feldspar grain boundaries that suggests a grain-boundary-softening effect contributes to the weakening. In addition, it is demonstrated that the presence of water does not lead to more microfractures, but to a reduction in the stresses required to initiate and propagate them.

Jan 1, 1982

Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

Last October a committee was appointed by The War Service Association of Manufacturers of Solder and Bearing Metals, Inc. to consider the report of the U. S. Bureau of Standards to the Conservation Division of the War Industries Board, a letter of the War Industries Board, and the discussions of this letter as reported at the meetings of association and to summarize the information thus obtained. The report of this committee has just been printed. The committee agrees with the Bureau of Standards that 99 per cent. tin can be used. It also finds that a very small amount of lead might increase the tendency of the bearing to crack and that lead has a hardening effect on babbitts up to a possible limit of 10 per cent. of lead. Still in the so-called genuine babbitts, in the presence of lead a certain proportion of low melting point eutectic is introduced which admits of the bearing being poured into thinner sections and is decidedly advantageous in the die-casting process in producing a much smoother casting. But the committee recommends that the Bureau of Standards thoroughly investigate this point. Lead-base babbitts, to give satisfactory service, must be carefully made of the proper raw materials. The bronze hearing that has been thoroughly tinned and containing the thinnest possible babbitt lining is now becoming recognized as the ideal bearing. The compositions, recommended by the committee are as follows:

Jan 2, 1919

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By B. R. Palmer, G. Gutierrez B., M. C. Fuerstenau

Selective flotation in nonmetallic systems is often complicated by the presence of iron-bearing silicates occurring as gangue. Minerals such as augite, diopside, hornblende, and tourmaline respond readily to flotation under the same conditions as ore minerals. Mechanisms by which these minerals respond to flotation with anionic collectors must be established if selective separations are to be made in these systems. It was the objective of this investigation to determine the mechanisms involved in the flotation of two pyroxenes, augite and diopside, with potassium oleate. Experimental Materials and Methods Pure potassium oleate, prepared by neutralization of oleic acid with KOH, was used as collector, while reagent-grade HC1 or KOH were used for pH adjustment. Conductivity water, made by passing distilled water through a mixed-bed ion exchange column, was used in this investigation. Two pyroxenes, [ ], were involved in this work. One member of this class of minerals was augite and was found to contain 3.3% calcium, 4.6% iron, and 9.6% magnesium. The source of this mineral was Tillamook County, Ore. The other pyroxene involved was diopside which contained 8.3% calcium, 2.7% iron, and 7.6% magnesium. The source of this sample was Bancroft, Ont. Microflotation experiments were conducted with a Hallimond cell. Mineral samples were ground dry and sized to 100 x 200 mesh. One-gram charges were conditioned for 3 min in the presence of various additions of potassium oleate. Flotation was conducted for 1 min with a nitrogen flow rate of 50 cm3/min. The electrophoretic mobilities of these two minerals were measured with a Zeta Meter in the absence and presence of [ ] salts and in the presence of an indifferent electrolyte, NaC1, added to maintain ionic

Jan 1, 1978

By Earl Bardwell

(Butte Meeting, August, 1913.) THE structural relations existing between cuprous oxide and copper were first systematically studied by Heyn1, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming .;from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study off the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing, this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in, this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity.

Jan 7, 1913

By Carl Scholz

Discussion of the paper of Carl Scholz, published in Bi-monthly Bulletin, No. 22, July, 1908, pp. 551 to 559. HOWARD N. EAVENSON, Gary, W. Va. (communication to the Secretary*) :-For some time before the publication of Mr. Scholz's paper, I had been collecting data bearing upon its subject, and I now take pleasure in presenting my results to the Institute in the form of a discussion. It has long been a matter of common opinion among mining-men that mice-explosions are, more frequent during the colder, or winter months, than during the warmer ones, and it is a matter of common knowledge among them that the air-ways and road-ways in most mines are much drier and are more in¬clined to be dusty during the winter than during the summer. In many mines, places which are wet and sloppy in the summer are dry and sometimes dusty during the winter. These changes, of course, can only be due to atmospheric conditions, and are caused by differences in temperature and humidity. Until recently, however, very little attention has been paid to the part that atmospheric conditions may play in mine-explosions, or, rather, to the effect they may have in rendering mine-conditions peculiarly dangerous, and in spreading and rendering more disastrous the effects of what would otherwise probably have been .small explosions. To show the difference in mine-conditions during sunnier .and winter months, I have tabulated in Table I. the results of 24 observations of hygrometric conditions in several different mines at different times of the year. Mines Nos. 1, 2, and 6 are located in the Pocahontas.coal -region, in McDowell couuty, W.Va., the first one being a shaft-mine shaft mine and the others drift. Mines 1A and 2A are drift-mines located in Logan county, W. Va. All of these are mines of fair size, but none of them has been in operation more than six years,

Jun 1, 1909

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.' Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph' (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,' have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By K. L. Meissner

IT is well known that the so-called pure aluminum contains noticeable amounts of impurities, chiefly iron and silicon, and many investigators have studied the forms in which these impurities exist. Hanson and Archbutt1 state that iron exists in aluminum as FeAl3 and silicon as elementary Si. The solubility of FeAl3 in solid aluminum is practically zero, or at, least so small that the smallest trace of this compound is always visible as a separate constituent. Under the microscope an untrained eye can hardly distinguish, without etching, the two constituents FeAl3 and Si, but they can be differentiated by suitable etching reagents. Anderson2 also found the same results. At the same time, Merica, Waltenberg, and Freeman3 found a constituent of unknown composition. They found a small thermal effect, at 610° C., on the cooling curves of aluminum with small amounts of iron and silicon. The intensity of this effect increased with increasing silicon content, until an effect occured at 576° C. due to the eutectic between aluminum and silicon. The authors ascribed the effect at 610° C. to a compound, which they call "X constituent." It was thought to be a ternary compound containing iron and silicon and could be observed under the microscope as dark particles. Dix4 has published unetched photomicrographs of an aluminum with 0.51 per cent. iron, 0.99 per cent. silicon, and 0.32 per cent. copper that shows three constituents: the dark Si (black in the figure), the lighter FeAl3, which appears in half tone and crystallizes in needles, and a constituent of the same color as FeAl3 but of different crystal form, often resembling Chinese script. This last constituent, Dix thought, is a compound of Fe and Si; not the compound FeSi but a compound containing a relatively small amount of silicon. Therefore an alloy of aluminum, iron, and silicon (the copper should not be regarded in the following considerations) must contain the following four constituents: Al, FeAl3,

Jan 1, 1926

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By Howard A. Meyerhoff

AS a source of mineral wealth, the larger islands of the West Indies have never had an enviable reputation. The Spaniards took possession of them in the sixteenth century hopeful that they would yield gold; but it was not long before they knew the rather rigid limitations of Antillean gold production and were seeking-and finding ---richer deposits of the precious metals in Mexico and on the west coast of South America. Although a great deal of wealth changed hands in the West Indian islands in subsequent years, the fact may be laid to the abundance of pirates and privateers and not to the richness of local ore bodies.

Jan 1, 1941

By John M. Sharp

John M. Sharp, Jr. (Assistant Professor of Geology, University of Missouri, Columbia, Mo.)-Geothermal gradient and surface temperature data anomalies are potentially useful tools in mineral exploration, These data, however, may reflect a number of geologic and hydrologic processes as well as the thermophysical properties of the geologic materials. The author presents a relatively simple model which may be of value in mineral exploration. The lack of consideration of other processes, however, limits its usefulness. For instance, because of erosion or sediment deposition over geologic time the land surface must be considered a moving boundary in such a model. Evaluation of this effect coupled with annual surface temperature and thermal conductivity variations can result in temperature profiles such as shown in [Figs. 4 to 7]. These effects and others, such as ground-water movement," must be considered and filtered from the data before proper interpretation is possible. Another assumption which should have been discussed is, why were the observed mean surface temperatures not used for extrapolation of the gradients in [Figs. 4, 6, and 7?] Conductive heat transport responds to the actual boundary (land surface) temperature, not to theoretical temperatures in the absence of perturbations. Benfield presents a theoretical model for calculating perturbations in the geothermal gradient for erosion and sedimentation. The temperature (T) at any time (t) and any depth below the surface (x) is given by [ ] where T is the mean surface temperature, G, the geothermal gradient, v, the rate of erosion (or sedimentation),[ ], the long-term rate of change of T0, and k is the thermal diffusivity of the rock. Using the author's values and a rate of erosion of 1.54 cm per yr for a period of 10,000 yr, a thermal profile as shown in [Fig. 10] will be generated. A thermal diffusivity of 0.0164 sq cm per sec was used, corresponding to a thermal conductivity of 0.0082 cal per cm per sec per C. In [Fig. 11], a sediment deposition rate of 3.0 cm per yr for a period of 1000 yr was used to generate the subsurface temperature profile. A surface temperature of 24.3°C was used, as specified in [Fig. 9, 7], was set equal to zero for both cases. Superposition on the generated profiles in [Figs. 10 and 11] of the annual surface temperature variation perturbation (which may be calculated in a number of ways) will yield profiles similar to those in [Figs. 4 and 7]. Similar profiles can also be produced by regional ground-water flow. Models like the author's can be of value in mineral exploration. Other processes, however, which affect surface temperatures and gradients must first be considered, calculated, and filtered from the data if anything but the crudest qualitative interpretation is to be made. Robert C. Edmiston (Author's reply)-Professor Sharp has raised three objections to my interpretation of the subsurface temperature data I collected at Silver Bell. These are: 1) No correction was made for erosion or sedimentation,

Jan 1, 1977

By J. J. Gilman

WHEN a zinc crystal is immersed in liquid N, and then plastically bent, it is observed that it bends a certain amount and then fractures. This fracture occurs at a fairly reproducible radius of curvature, and the radius varies systematically with the crystal orientation. Because this phenomenon provides an unusually well-defined set of fracture conditions, it is possible to examine various possible fracture criteria and select the best one. Zinc crystals of various orientations were bent about axes lying in their glide planes (0001) and perpendicular to their glide directions [1210]. The crystals were 0.150 in. diam and had chemically polished surfaces. They were immersed in liquid N, while they were being loaded on an Instron testing machine. A three-point bending jig was used to load them. Table I lists the beam radius at which fracture occurred for each orientation. Each value is the average of at least six measurements. The normal stresses on the cleavage planes, at the time of fracture, were calculated as follows: First, from the fracture radius, R,, the orientation angle, x,, of the (0001) plane at the outer fiber was calculated. If x, = angle between the (0001) and the rod axis prior to bending, d = rod diameter, and X, = angle between the (0001) plane and a tangent to the bent crystal, then1 sinX, _ 2R, sin xn 2R, + d Since the glide shear strain is given by' y ' cot X, — Xo the glide strain at fracture, x,, can be calculated. Next, it is necessary to know the tangential stress in the outer fiber at fracture. This depends on the plastic flow curve, so a series of tensile tests were performed at —196°C on another set of zinc crystals. A curve of the average resolved shear stress versus glide strain was prepared. From this curve, shear stresses, r,, corresponding to the glide strains in the bend tests were taken. These values are listed in Table I. Then the normal stresses in the outer fibres, u,, were calculated from the relation U, = r, tan X, This analysis assumes that the fiber stresses in a bent beam are the same as the stresses in simple

Jan 1, 1959

By Eugene Coste

Although some of the observers who first paid especial attention to the occurrences of oil and gas in the strata (such as Hunt in 1859, Andrews in 1861; Winchell in 1865, Mendelejeff in 1876, Höfer in 1876, Minshall in 1881, and I. C. White in 1883) seem to have been impressed with the fact that oil and gas deposits were connected with the disturbances in the rocks caused by their upheavalll yet, with the exception of Mendelejeff, and possibly Andrews, these observers do not appear to have understood what is really the one essential factor in the occurrence of oil and gas in the strata: viz., the faulting, uplifting, fracturing, fis-suring, and jointing always accompanying even slight rock disturbances, and in certain districts (petroliferous provinces)2 allowing solfataric hydrocarbon emanations to force their way up from the interior and to reach and impregnate the porous portions of sediments subjected to the disturbances. Instead of this simple explanation to account -for the observed connection between petroleum deposits and rock disturbances, most of the observers mentioned above, and many others who have foliowed them on the same lines since, have entirely reversed the problem. To them, instead of the dissemination of gases from fissures into the sediments, it presented the accumulation and concentration, according to anticlinal or other geologic structures, of oil and gas originally present throughout the whole mass of the strata where they were produced by the decomposition or distillation of organic remains. Whether this important problem involves accumulation from sources within the strata themselves, or infiltration and dissemination from outside sources, may be easily determined if all preconceived ideas are put aside and the established facts only are considered. Physical Facts Sedimentary strata are composed of alternate beds of shales, sandstones, and limestones, most of which are sufficiently close-grained to

Jan 1, 1915

By N. L. Hancox

Previous researchers have used the cutting and rejoining model to represent a porous body when attempting to place Archie's law on a theoretical basis and calculate rock permeabilities (F = Ø-m, where F = formation factor, = - porosity and m = a constant). In using the model, a porous solid is assumed to consist of sections with parallel sides containing straight. continuous pores of total porosity 4 (pore to total volume or, for a homogeneous body, pore to total area). The joining of pores at an interface between two sections is assumed to be random which results in a common pore area Ø2. This reduced area Ø2 is then taken as that area which limits electrical conduction or fluid flow in the body. Agreement between experimental results and results calculated using a model is not always good Because of this, various modifications of the model are presented — for instance, the random nature of the joining is questioned. Formation factor measurements on specially constructed porous specimens are described in this paper. it is concluded that the common pore area limits flow completely only if sections containing straight pores are very thin, and that, in most natural materials, the common pore area at an interface must be greater than that given by random joining. However, the model is still useful in permeability calculations, provided that the fractional area limiting flow is determined from formation factor measurements. INTRODUCTION Two important properties of porous media are permeability k, which describes the ease with which a fluid can flow through a porous medium, and formation factor F, defined as the ratio of the resistivity of a saturated specimen to the resistivity of the saturating liquid which describes the electrical properties of the saturated material. k is defined by Darcy's law,l k= µqL/P Ae . . . . . . . . . . . . . . . [1] where µ = liquid viscosity, q = flow rate, L = length of specimen, p = pressure across the specimen and = - the effective area over which flow occurs, F is given experimentally by Archie's law,2 F = Ø-m ,..............(2) where 4 is porosity defined as the pore to total volume or, for a homogeneous body, the pore to total area; and m lies between 1.3 for loose sand and 2 for cemented sand. Consider a porous body of total cross-sectional area A and length L, saturated with a liquid of resistivity R and with an effective area for conduction of Ae. Then, from the definition of F given previously, F=A/Ae , ................(3) or, from Eqs. 2 and 3, Ae = A Øm ..............(4) Thus, in any attempt to calculate k or F, some assumptions must be made concerning the pore structure of the body and a value derived for A,. To determine Ae, Childs and George3 and Wyllie and Gardner4 suggested an elementary statistical representation often referred to as the cutting and rejoining model of a porous body. The body is assumed to be composed of two or more parallel-sided sections of porosity 4, containing straight, continuous pores with a common pore area of Ø2 at an interface between two sections. The value is given by a random joining of the pores in either section. Two such sections,

Jan 1, 1969