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By G. T. Pruitt, T. L. Irby, P. B. Crawford, H. Ferrell

In water flooding peripheral, center-to-edge, line-drive or water-encroachment patterns the question has arisen, "when should a producing well be converted to a water-injection well?". It is realized that, if the producing well is shut in when water breakthrough occurs, some oil could be left in an unswept area. Yet, operation to high water-oil ratios may require processing much additional water. If a well is shut in, "where should the allowable be transferred?". A review of the literature indicates that very few data are available to the engineer to assist him in answering these questions. It is the purpose of this paper to present information which may be of value in selecting the flooding technique and the injection and producing wells and in scheduling injection and production rates. Certain phases of these problems can be studied in the laboratory. The Potentiometric model is well suited for studying many waterflooding problems. This model assumes that steady-state flow exists, that the mobility ratio is equal to one and that gravitational effects are neglected.'-' The three-phase sand model also has been recognized as an effective means for studying certain reservoir problems. Both models were used in making the study reported here. This paper discusses seven cases utilizing various waterflooding techniques. Data for the first five cases were obtained on the potentiometric model. Data for Cases VI and VII were obtained by constructing and flooding an unconsolidated sand pack (a three-fluid-phase system) and by determining the swept area and cumulative oil recovery for various types of operations. APPARATUS AND PROCEDURE The potentiometric model reservoir was 30 in. long X 10 in. wide by about 1/2 in. deep. Four wells were equally spaced in a line array along the lateral center line. (See Fig. 1.) Well No. 1 initially was an injection well for each of the patterns reported. The cases studied with the potentiometric model and sand model are described herein. The laboratory sand model reservoir was a 30- 10-in. rectangular Lucite vessel packed with sand to a depth of about 0.65 in. Four wells were equally spaced in a line array along the lateral center line. The reservoir material was an unconsolidated sand into which the reservoir fluids were mixed to yield fluid saturations of 55 per cent oil, 25 per cent water and 20 per cent gas. The water was added to the sand and the material mixed, after which the oil was added. Kerosene and water, the fluids used, gave a viscosity ratio of 1.64:1. In packing the reservoir, care was taken to assure constant fluid saturations and constant porosities. A new mixture was prepared for each run. During water flooding, a colored water was injected by a constant rate pump. The injection rate was 1.1 B/D/ft of sand thickness. For this series of tests, each of the producing wells was open to the atmosphere and, as in the potentiometric model study, Well No. 1 initially was an injection well for each of the patterns. KESULTS OF POTENTIOMETKIC MODEL STUDlES Two cases (Cases I and 11) involving equal pressure injections were studied, with the following results. Case Water injection was initiated at Well No. 1; the producing wells (Nos. 2, 3 and 4) were operated at constant and equal bottom-hole pressures. When water broke through at Well No. 2 and achieved the selected water-oil ratio, Well 2 was converted to a water injection well, resulting in two injection and two producing wells. The injection pressures at Wells 1 and 2 were maintained equal and constant; pressures at the producing wells were held equal, but they were lower than those at the injecting wells. A similar process was repeated when water broke through at Well No. 3. The flood was terminated when

By J. T. Michalak, H. W. Paxton

The recovery of the initial flow stress of poly-crystalline iron is characterized by a) a logarithmic time dependence; b) an increasing activation energy with increasing recovery; c) an increased ?,ate and fraction of recovery with decreased temperature of deformation; and d) an increased rate with increased deformation. Isochro)ml studies of the recovery of single crystals revealed more sluggish recovery. The original flou3 stress of single crystals could be regained by recovery anneals at 800"or 900°C. ThE great majority of the theoretical treatments and experimental studies of strain-hardening have been concerned with the close-packed lattices.' Very little effort has been expended on the bcc structure so that the theory of work-hardening of this lattice is essentially nonexistent. The limited amount of experimental data resulting from the direct studies on silicon-iron,2 low-carbon steel,3 and purified irons4"7 does not as yet permit a detailed analysis of the strain-hardening. Studies concerned with the effects of annealing following deformation have been few in number," have been somewhat limited in extent, and have had the disadvantage of using irons containing a substantial impurity content. The present research was undertaken to augment the limited knowledge we have of the characteristics of a bcc metal as regards strain-hardening and recovery from the strain-hardened state. The recovery of the flow stress has been employed since it was felt that the stress associated with the hardened state gives at least a fair qualitative description of the state of the imperfections causing the hardening. The study was concerned primarily with the recovery of flow stress following strain-hardening of polycrys-talline, zone-melted iron as a function of the amount of deformation, the temperature of deformation, and the time and temperature of the recovery anneal. A limited investigation of the recovery of the initial flow stress of single crystals of this same material as a function of the recovery temperature was also conducted in conjunction with the Lambot X-ray technique." MATERIAL The zone-melted iron used in this investigation was obtained through the courtesy of the American Iron and Steel Institute and Battelle Memorial Institute. The analysis, as given by the supplier indicated a maximum impurity content of 0.02 wt pct excluding those impurities listed in Table I. (The actual impurity content is very probably less than this since detection limits were considered as the amount of a particular impurity level.) Also listed in Table I are the interstitial impurity contents of the iron at various stages of experimental work indicating that these im-

Jan 1, 1962

By Carl E. Swartz

For many years kettles used in the melting and refining of lead and other nonferrous metals and alloys have been made of cast iron. The logic of this probably lies in the fact that cast iron has been known as a material of construction for vessels of this type much longer than steel, and satisfactory fabrication from it has been more easily accomplished and better understood. As the capacity of lead refineries has increased, it has been only natural to increase the size of kettles. Today kettles of 150 to 250 tons are not uncommon. As the size of the kettles increased and better shapes were designed, the uniformity of material of construction became more important. Records kept over comparatively long periods of time have shown that the length of service of kettles has not been uniform. Many causes contribute to this and the importance of each has not yet been evaluated. Kettle design, kettle setting, method of firing and material of construction have been changed from time to time to obtain better service, but the variation in length of service is still great. A kettle may fail during the first few heats or may last through more than one thousand heats. The purpose of this article is not to present the conclusions of a finished piece of research on kettle manufacture and use, but to present a series of observations made over considerable time in the hope that others will publish data and that all may be correlated into a logical scheme which will result in better service and longer kettle life.

Jan 1, 1931

By Irving Hale

The superiority of electric power for mining purposes was recognized in a general way as soon as the electric motor be-

Jan 1, 1897

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.' The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.'-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By J. P. Matoney, E. J. Sandy, D. A. Dahlstorm

INTRODUCTION Before an understandable discussion concerning coal-dewatering processes can be initiated, it is necessary to define some terms of usage. The many different meanings and interpretations of terms preclude development of standard definitions so that the terms which are defined in this chapter should be regarded mainly as working terms intended to facilitate communication. A coal slurry ' might be defined as a watery suspension carrying particles of fine coal and other assorted material ranging upward in size from the finest clay particles. Some particles may be in the colloidal sue range and exhibit characteristics of suspended colloids. The dilution of the system generally is such that it is in a condition of independent particle subsidence. In some coal mining areas a slurry is regarded as a suspension of fine coal and other materials having a dilution that cannot be economically dewatered by filtration. A coal slime may be regarded as a slurry containing particles of such size range that 50 per cent or more (by weight) will pass a 200-mesh sieve. Slime suspensions generally are difficult to handle without special treatment in conventional sedimentation equipment. A coal sludge is defined as a slurry that has been partly dewatered by sedimentation usually to a thick or viscous consistency where further dewatering can be most readily facilitated by filtration. Culm and silt are terms characteristic of coal-preparation practice which should be defined. In anthracite terminology, culm is the generally coarse residue or waste accumulation of coal, bone and rock from preparation plants most of which are no longer functional. Culm has a wide range of sizes, some rather coarse, and except to differentiate it from silt, the term is of limited interest in this discussion. In anthracite terminology, silt is the accumulation of waste fine coal, bone and slate settled out from preparation plant water in excavated basins. Silt is generally made up of particles ranging in size from 3/32-in. round-opening screen to the very finest sues. Silt is also referred to at times as sludge, fines, slush, and mud and is the partly dewatered derivative of what has been previously defined as slurry. In the terminology of the bituminous coal producing areas, the word culm commonly corresponds to slurry or slime, depending upon the size distribution of the suspended solids. Editor's Note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections authored by each individual as is the case in most chapters of this book.

Jan 1, 1968

By John T. Norton, Robert J. Anderson

The purpose of this paper is to report evidence, regarding metal structures, that is contradictory to the amorphous-metal hypothesis of Beilby, and particularly evidence that is opposed to the proposition that a vitreous amorphous layer is produced by polishing a piece of metal. According to the theory of Beilby, which has been developed by Rosenhain and others, polishing a piece of metal greatly affects the condition of the metal at or near the surface polished, making that surface entirely different in character from the metal beneath. A vitreous amorphous surface film is said to be formed. The polishing process, on the basis of Beilby's explanation, is well known and does not require discussion here, but it is advisable to seek the precise meaning of the term "amorphous." According to Beilby, "amorphous means non-crystalline in the most intimate sense of the word; the molecules arc not marshalled in crystalline order and orientation." According to Rosenhain, the amorphous condition is that assumed by a metal when the crystalline arrangement is completely broken up so that the atoms exist in a state of disorderly arrangement similar to that which exists in the liquid state. Thus, from the point of view of the phase rule, the "amorphous phase" is regarded as being identical with the liquid phase. Amorphous metal is often likened to an undercooled liquid. A crystalline substance is one in which the atoms are arranged in space according to some definite repeating geometrical pattern. The existence of amorphous metal has not been definitely proved. The evidence offered here that amorphous metal probably does not exist is of a direct nature and is afforded by x-ray diffraction effects given by a number of metals and alloys when polished, cold-worked, and annealed. Considerable of the experimental work was carried out with substantially pure aluminum and the aluminum alloy duralumin, but many of the observations made on these materials were checked by similar observations on copper, iron, tin, zinc, lead, mild steels, and

Jan 1, 1925

By D. T. Peters, C. R. Cupp

Aging of commercial 18 pct Ni maraging steel and of related binary, ternary, and quaternary alloys has been studied by electrical resistivity, X-ray diffrac-tion, and hardness measurements. The aging process is in three stages: 1) recovery of martensite; 2) two precipitation reactions; 3) formation of nickel- rich austenite. The main objective of this work was to discover the nature of the Co-Mu interaction. Addition of cobalt to the Fe-18 pct Ni-5pct Mo alloy results in acceleration of the pvecipitation reaction by increasing the super-sat~lration 0f molybdenum. The cobalt-containing al- loys show no incubation period for the precipitation reaction, but the alloy without cobalt shows an initial slow reaction. These results are interpreted in terms of precipitation on dislocations. At low aging temperatures, the presence of cobalt leads to the appearance of a second type of precipitate which is a particularly effective hardener. Cobalt was found to retard the formation of austenite. Overaging is a combination of classical overaging and the formation of austenite in the structure. he- activation energy for the precipitation reaction determined from resistivity ,measurements is 42.8 kcal per mole and the growth of the precipitate is found to obey at law at high tenzperatures and a tU3 law at low temperatures. HE mechanism of strengthening of the 18 pct Ni maraging steels has been studied extensively since 1962.'-? The strengthening is due to precipitation hardening of the martensitic matrix. The main precipitate is an inter metallic compound involving molybdenum, but there is disagreement about its identity.

Jan 1, 1967

By C. L. Bulow

In this discussion of stress-corrosion cracking of widely used copper-base alloys, no attempt has been made to prepare an extensive review or bibliography since this has been quite ably covered by other investigators. An excellent bibliography was published by H. P. croft(1)2 in connection with his studies of stress-corrosion cracking in mercurous nitrate solutions and his analyses of the magnitude and distribution of stresses in brass parts. We are reporting on a few of the results which have been obtained to date in connection with an ammonia vapor test and an alternate immersion test. These are accelerated corrosion tests for determining the susceptibility of materials to failure from season or stress-corrosion cracking due to the presence of moist ammonia and oxygen so prevalent in nature. Our experiences with the ammonia test seem to indicate that it is a more searching test, than the mercurous nitrate test.

Jan 1, 1945

By T. E. Leontis

Data are presented in this paper to show that addition of zirconium to sand-cast Mg-Th alloys effects a marked decrease in the grain size of these alloys which is accompanied by a significant increase in the mechanical properties over the entire range of thorium content investigated. The beneficial effect of zirconium on the strength properties is maintained at elevated temperatures up to 700°F. In addition the alloys exhibit exceptionally high creep resistance at temperatures up to 600°F. Zirconium does not greatly improve the strength or creep characteristics of extruded Mg-'Th alloys. Cerium is not a desirable addition to Mg-Th-Zr alloys. IN a previous paper,' it was shown that addition of thorium to magnesium imparts exceptionally high resistance to creep at elevated temperatures both in the sand-cast and in the extruded states. The large grain size of the sand-cast alloys, however, renders them of questionable value as engineering materials. Sauerwald² showed that the grain size can be reduced effectively by the addition of zirconium. Results of a detailed study of the properties of Mg-Th-Zr alloys over a wide range of thorium content are presented in this paper. In accordance with the preliminary findings of Sauerwald,² it is shown here that Mg-Th-Zr alloys possess the unusual combination of fine grain size and a high level of strength and creep resistance at elevated temperatures. Some information on the effect of cerium on the properties of Mg-Th-Zr alloys is presented also. Effect of Th on Solubility of Zr in Molten Mg Sand-cast test bars and 3 in. diam extrusion billets of Mg-Th-Zr and Mg-Th-Ce-Zr alloys* were pre- pared according to the procedures described in the previous paper.' The zirconium was added in the form of sponge metal as supplied by the Bureau of Mines.' The maximum amount of zirconium that usually can be introduced into magnesium at the customary alloying temperature of 1350° F is about 0.7 pct. The analyses in Table I clearly show that thorium in- creases the solubility of zirconium in liquid magnesium. The tabulated zirconium contents are designated as "acid soluble;" this serves to distinguish these values from the small amount of zirconium that is not dissolved when the alloy is subjected to the action of a dilute acid solution. The "acid-insoluble" zirconium is believed to be ineffective as an alloying ingredient. The acid-insoluble zirconium contents ranged between 0.03 and 0.16 pct in the present alloys, the tendency was toward higher values in alloys with higher thorium content. In contrast to the effect of thorium, cerium decreases the solubility of zirconium in magnesium. This is shown by the three Mg-Th-Ce-Zr alloyst in- cluded in Table I and stands in agreement with the observations of Nelson and Stricter".' on Mg-misch-metal-Zr alloys. Effect of Zr on Grain Size of Mg-Th Alloys The potent effect of zirconium as a grain refiner has been demonstrated for many types of magnesium alloys.3-8 Of greatest importance to date are Mg-Zn-Zr alloys5,6,8 and Mg-mischmetal-Zr alloys.3,4,7 Zirconium has also been found to exert a marked grain-refining action on Mg-Th alloys. All the Mg-Th-Zr alloys cast in the form of ½ in. diam test bars have an exceedingly fine grain size (Table I). Reference to the previous paper' will show that binary Mg-Th alloys containing up to 6 pct Th are almost completely columnar even in the M in. diam reduced section of a test bar, and that 10 to 50 pct Th alloys have an equiaxed grain structure of 0.03 to 0.08 in. The data in Table I also show that addition of cerium to Mg-Th-Zr alloys has no effect on the grain size. In addition to increasing the strength properties, the fine grain size of Mg-Th-Zr alloys

Jan 1, 1953

By A. E. Worthington, R. F. Meldau

An analog computer study was made of the reduction of the magnitude of the SP by formation geometry and resistivity effects. Practical field .situations were studied. The analog data were converted to the form of departure charts. These charts may he used to determine the reduction in the SP due to the above eflects pith good precision Quantitative interpretation of the SP log in terms of formation water resistivity is presently based on the premise that the observed SP is equal to the electrochemical potential developed across a shale between the mud filtrate and the formation water. This procedure inherently assumes that, first, no electro kinetic (streaming) potential is present, and, second, that the SP is not reduced by resistivity or geometry effects in the formation. When, however, such a reduction of the observed SP does occur, one may write, SP = b,E, b, E, (1) where SP is the observed self-potential opposite the center of the bed under consideration. In this case, E, is the electrochemical potential, E, is the electrokinetic potential, b, is the electrochemical reduction factor, and h, is the electrokinetic reduction factor. The first assumption above is equivalent to assuming E, = O in Eq. 1 and the second assumption is equivalent to h, = b, = 1. Examination of electric logs shows that for many formations of interest the observed SP is reduced below its maximum value. The object of this work is to aid quantitative SP interpretation in at least some of these situations by obtaining values for b, and b, in Eq. 1 as functions of realistic combinations of bed thickness, depth of invasion, and formation resistivity. The only previously published work in this field known to the authors is by H. G. Doll' in 1948. He evaluated b, under conditions permitting exact analytical solution. His work clearly established the importance and qualitative nature of formation geometry and resistivity effects upon the SP, but the necessity of obtaining analytical solutions restricted his study to situations of limited practical interest. In order to extend such studies to practical combinations of formation parameters which do not lend themselves to feasible analytical solutions, the results reported in this paper were obtained by use of a special analog computer. THE ANALOG MODEL The analog model used for this study was the Guyed Analog Computer which originally was designed and built for resistivity log departure curve studies. It consists of a two-dimensional mesh of resistors, with the vertical mesh corresponding linearly to vertical distance along the borehole, and the horizontal mesh corresponding to radial distance from the borehole axis. By proper choice of horizontal resistor values, a three-dimensional, axially symmetric, borehole-formation problem can be modeled with this two-dimensional array. These and other details of the model are contained in a paper by H. Guyod'. The geometry used for the SP studies with the analog is depicted in Fig. 1. This configuration has a horizontal plane of symmetry, and, hence, the model, and the following discussion, need only to be concerned with one quadrant such as shown in Fig. 2. A further simplification arises by considering that both the natural potential sources and those used in the model have fixed internal impedance. Therefore, the current flows produced by these sources can be separated and studied independently ( i.e., the superposition theorem can be applied). SP = SP, i SP, = h,E, + b,E, ,(7)

By J. O. Brittain, E. P. Lautenschlager, F. Felberbauer

This investigation was undertaken to evaluate the effect of a dispersed phase in a iron upon the strain hardening and the stress dependency of dislocation velocity as inferred from the strain-rate sensitivitv. Experiments were made in a-iron specimens with controlled amounts of carbon and/or A12O3. They were tested at various temperatures between 195' and 373 'K under a variety of conditions oj-concentration, strain rate, and quench aging. The resulting yield strength, flow strength, and strain hardening increased with addition of Al2O3. The parameter m, measured from changes in strain rate, was xsed to describe the stress dependency of the dislocation velocity. m was found to increase with additions of A12O3, increasing carbon in solution, and with increasing temperature. When applied to a recent model for yielding based upon dislocation multiplication and velocity characteristics, the values of m alone did not successfully predict yielding for the materials of this investigalion, but had to be adjusted with a consideration of the number of unlocked dislocations nucleated heterogeneously at discontinuities or inclusions. The change of yield strength with Al2O3 Interpar-ticle spacing appeared to obey a theory of Orowan. EVER since the concept of dislocations has been introduced to explain plastic deformation in crystalline materials, the origin of dislocations and the source of the number of dislocations required to account for plastic deformation have been persistent questions. Ruling out the possibility of homogeneous nucleation,' Gilman2 drew attention to the various cases of heterogeneous nucleation as the source of dislocations, whereas Frank and Read3 introduced the Frank-Read source. However, Gil-man found that the Frank-Read sources did not play a dominant role in the deformation of LiF crystals, but that small precipitates are often, if not always, associated with the nucleation of dislocations. In LiF crystals, however, most of the dislocations arose through the multiplication of moving dislocations in a mechanism described by Koehler4 and Orowan,5 Thus, relatively few precipitates could account for a large number of dislocations. A similar observation of dislocation nucleation at inclusions of precipitates was made by Stein and LOW' on Si-Fe crystals. Their crystals contained

Jan 1, 1964

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By Charles S. Barrett, Frederick N. Rhines, Robert F. Mehl

The solid solutions which aluminum forms with copper, and with magnesium and silicon, are not extensive, and accordingly could not be expected to form Widmanstatten figures profusely nor with great ease. A study of the Widmanstatten figures in these systems seemed desirable, however, because of the interest which these alloys bear towards age-hardening theories resulting from the necessary relationship between the age-hardening phenomena and the atomic processes leading to the formation of Widmanstatten figures.' Alloys of Aluminum with Copper The most accurate determination of the solid solubi1it.y of copper in aluminum seems to be that by Dix and Richardsoq2 whose results are represented in Fig. 1. According to this work, aluminum dissolves 5.6 weight per cent of copper at 548", and less than one per cent at room temperature. Judging from the constitutional diagram, this solid solu-lion on cooling tends to precipitate the compound CuA12, and this conclusion has been confirmed experimentally by Schmid and Wassermann.

Jan 1, 1932

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By E. P. Polushkin

This work has for its purpose the establishment of a new method for determining the structural composition of alloys. The area occupied by a constituent on a few representative photomicrographs of the alloy is measured, by a planimeter, especially designed for metallographic work, and the volume and proportional weight of the constituent calculated. Experiments have shown that the results are accurate enough to justify the application of the method to many problems in metallographic research instead of chemical analysis. The advantage of the method is the possibility of determining the amount of the constituents without separating them from the alloy; their composition may also be determined if the ultimate chemical analysis of the alloy is known. Suppose Fig. 1 represents a part of a photomicrograph on which the total area of the black figures is to be found. By a system of parallel lines drawn short equal distances apart all figures may be divided into trapezoids. As the area of a trapezoid is equal to its median multiplied by its altitude, the relation between the total areas of the black and the white figures comprised within each strip is equal to the relation between the sums of medians for these figures respectively. This is also true for the whole area of the photomicrograph. Therefore, to determine the total areas of the black and white figures we must first find the proportion between the sums of the medians and then divide the area of the whole photomicrograph in the same proportion.

Jan 1, 1925

By John D. Sullivan

Leaching of copper ores is a comparatively old art, probably dating back to medieval times. The leaching of mixed oxidized-sulfide ores, however, is modern. The first modern plant leaching mixed ores was at Ajo, Ariz., where commercial operations commenced in 1917. While the ore at Ajo was primarily oxidized there was always some sulfide present. The Inspiration leaching plant, which was put in operation in 1926, may be considered the first plant constructed for the extraction of both sulfide and oxidized copper. The pioneers in leaching mixed ores had a difficult task before them since they had very little fundamental data on the chemical and physical factors of leaching. For the very large amount of painstaking experimental work that was done before building the Ajo and Inspiration leaching plants the reader is referred to the original articles.' For a period of several years the writer worked on problems connected with the chemistry and physics of leaching mixed oxidized-sulfide ores. This paper summarizes the experimental work and discusses various factors involved in leaching ores. It also presents many data heretofore unpublished. Among the new data are those on chrysocolla, pages 518 to 519, inclusive; dioptase, page 519; covellite, page 529; virtually all those on chalcopyrite, pages 531 to 533, inclusive; enargite, page 533; and tetrahedrite and tennantite, pages 534 and 533. The oxidized copper minerals of commercial importance in American ores are azurite, Cu3(OH)2(CO3)2; malachite, Cu2(OH)2CO3; chrysocolla, CuSi03.2H2O; tenorite (or melaconite), CuO; and cuprite, Cu2O. Dioptase, CuSiO3.H2O is less common. Brochantite, CuSO4.3Cu(OH)2, while the chief mineral in the ore at Chuquicamata, is not of major importance in the United States. Metallic copper, while chemically not so, is frequently classed as an oxidized mineral of copper. The most important sulfide minerals are chalcocite, Cu2s; covellite, CuS; bornite, Cu5FeS4; and chalcopyrite, CuFeS2. Less important complex sulfides are enargite,

Jan 1, 1934

By L. G. Huntley

I. HISTORY OF OIL DEVELOPMENT IN MEXICO THE occurrence of oil or "tar" in Mexico was mentioned as early as the seventeenth century by Friar Sagahun, who gives the Indian name "chapopote," by which these asphalt seepages are still called. This asphalt was apparently used, as it has been used by primitive people in many parts of the world, in religious ceremonies and for medicinal purposes. Travellers also report that the ruins in Yucatan and the pyramids in southern Mexico show traces of the use of "chapopote" as a building cement.1 DeGolyer says that the first attempt to exploit oil or gas in Mexico in a commercial way is shown by the records of the Memoria de Fomento of 1865, when permission was granted to a Senor Ildefonso Lopez to exploit the deposits of petroliferous substances in the San Jose de Ias Rusias area in the State of Tamaulipas. Other concessions follow, and probably refer to surface seepages which occur in that district. This was several years after the discovery of oil in Pennsylvania. In 1868, a well 125 ft. deep was drilled by a company organized in Mexico City, in what is now known as the Furbero district, and a little oil was refined there. In 1873, residents of Tampico denounced seepages along the Tamesi River, and asphalt was mined near Tempoal in the Canton of Tantoyuca. No drilling was attempted. But between 1880 and 1883 several shallow wells were drilled for oil in Mexico, two of them being near the present Potrero de Llano field west of Tuxpam. The wells were drilled by a Boston company with Canadian rigs, and are said too have reached a depth of about 400 ft., while one is reported to have flowed. Several other abortive attempts were made to drill for oil between 1885 and the beginning of the present century, about which time the Mexican, Petroleum & Liquid Fuel Co., Ltd., in which Cecil Rhodes was interested drilled 24 wells unsuccessfully, several of them as deep as 1,500 ft., in the State -

Jan 9, 1915

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride'-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962