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By John V. Beall, William F. Haddon

A long the mighty Andean Cordillera, there is splendor beyond imagination-in the natural beauty of the mountains and in daring engineering and lavish investment in the mines. This is the story of the great copper mines of Chile and Peru. Each mine has a special quality which has tested the physical and spiritual resources of the founder. In the early days of the older mines, the mining engineer of song and story was more the rule than the exception. He was physically tough, ingenious and a leader of men. In the current political and social environment of Chile and Peru, the foreign contract mining engineer is still needed; but he must be a different type of man. To John J. Selters at Cerro's Rio Blanco, the principal ingredient is still "toughness," but it is "toughness of mind" that is needed. "He probably should be a teacher." The copper mines are not new. They were, almost without exception, worked by Indians (La Exotica might prove the rule), and later by the intrepid Spaniards. Modern mining began after the turn of the century. In Chile, the first of the big ones was the Braden Copper Co. founded on the El Teniente deposit. This development was followed by Chile Exploration Co. at Chuquicamata and Andes Copper at Potrerillos. These properties have been developed over the years by vast expenditures of money and a monumental amount of labor. None was free of technical problems-metallurgy at Chuqui, marginal grade of the old mine at Andes, avalanches and the great fire at El Teniente. The evolution which has brought the established mines of Chile, and the new ones coming on stream, to their present state of development is in reality the work of wonders of input-money, engineering and responsible management in an atmosphere of political stability. Without any one of these, the result would have been failure.

Jan 11, 1969

By Louise Barton Freeman, Coleman D. Hunter

The total production of oil in Kentucky during the year 1943 reached 7,010,776 bbl., which is more than at any time since 1930. Of this total, 5,287,659 bbl. was produced from the counties west of the Cincinnati arch, 692,359 bbl. from the 18 new pools opened during the year, and 3,260,765 from the Smith Mills pool, which was discovered in August of 1942. This is an important increase in western Kentucky in spite of the low price of crude, and demonstrates effectively the desire of the industry to cooperate in meeting the increased demands made by the war. Western Kentucky Two deep tests were drilled in the Kentucky portion of the Mississippi Embayment this year. Both were drilled to test the St. Peter. One well, drilled in Marshall County by the Adams Oil and Gas Co., did not encounter any St. Peter sandstone but drilled 650 ft. of formation below the position of the St. Peter and above the true Knox dolomite. The other well, in Ballard County, was reported to have tested the St. Peter and to have been temporarily abandoned at 3069 ft. At this depth the well probably was stopped in about the same formation as the Marshall County well. No accurate information is available on the Ballard County well. Several new producing areas were added to the list of fields in the western Kentucky coal basin, in Daviess, Henderson, McLean, Ohio, Union and Webster Counties. The Smith Mills pool was enlarged and production was found in the McClosky (Ste. Genevieve) in addition to the Cypress sandstone from which much of the earlier production had been obtained. There was some interest during the year in testing the Devonian and Silurian formations in the area south and east of the western Kentucky coal basin. In the fall of 1943, a 15 to 20-bbl. well was drilled in Allen County and two more wells are now being drilled. The production was obtained from within a few feet of the base of the Chattanooga black shale, probably in the upper Silurian. One well in Simpson County was drilled completely through the Silurian section before it was abandoned. Several wells were drilled in Logan, Todd and Christian Counties to test the Devonian where it is thinned by removal of the upper formations before deposition of the Chattanooga shale. None of these wells was successful but several other locations are now being tested. The Silurian thins in like manner on the eastern flank of the coal basin as the crest of the Cincinnati arch is approached, and it is along this thinning edge that such fields as the LeGrande, Logsdon Valley, Magnolia, Bowling Green and the Barren County pools were developed. A number of wells were drilled around these old pools in an effort to extend them, some of which were successful. The wells listed this year in Larue, Hardin, Barren, Hart and Warren Counties were drilled in the search for other such fields.

Jan 1, 1944

By T. A. Dungan

THE thermal processes for the production of metallic magnesium can be divided into two general classifications, the direct reduction of magnesia with carbon and the indirect reduction of compounds of magnesium by reducing agents that are themselves products of carbon reduction. The latter are so chosen as to cause reduction of magnesium compounds wherein only the magnesium is liberated in the vapor phase. Reducing agents used are: calcium carbide, silicon carbide, silicon, aluminum, various silicides or combinations of calcium, aluminum, silicon in iron. All of these are products of highly endothermic reactions and, with the exception of scrap aluminum, can be produced in an open, submerged arc furnace; that is, the arc is covered only by the charge itself. The more investment in energy required to prepare such a reducing agent, the less is the energy required in the subsequent step to reduce the magnesium compound to the metal. It is impossible, however, to avoid the laws of thermodynamics, no matter how much circumambulation is resorted to in the preparation of successively more powerful reducing agents. Since each such step carries forward its own inefficiencies, it appears evident that the ultimate status of such processes is dependent upon the development of by-products. EARLY EXPERIMENTS IN DIRECT REDUCTION The direct reduction of magnesium oxide by carbon has a decided appeal to both the scientist and the industrialist. The successful production of the carbothermic plant at Permanente is a significant fact in the substantiation of this concept. Like most developments, however, the history of carbon reduction of magnesia is not one of triumph after triumph, or immediate heady success to the investigators. It is understood that one of the early investigators conducted an experiment wherein he placed carbon and magnesia in one end of an evacuated tube and managed to heat this end to a temperature high enough that magnesia and carbon deposited at the other end of the tube. The charge, unreduced, appeared to have been completely transported from the hot to the cold end of the tube. This raised doubt for some time as to whether magnesia could be reduced at all with carbon. It was correctly suspected, however, that the magnesia was in fact reduced and the resultant magnesium vapor and carbon monoxide reacted upon one another upon reduction in temperature to reform the starting ingredients. Attempts were then made to dilute the two vapors by passing a considerable stream of hydrogen through an arc furnace charged with magnesia and carbon. Thus by dilution of the products it was expected to obtain metallic magnesium. The results were positive and metallic magnesium was

Jan 1, 1944

By Owen F. Devereux

Two discrete types of microstructure me seen in cermets formed by the reaction: 4Al (liquid) + 3SiO2 (glass) — 2A12O3(a) + 3Si (solid) Relatively coarse-grained macroscopically isotropic specimens resulted from reaction with aluminum containing appreciable silicon, while macroscopically anisotropic fine-grained specimens were formed by reaction with aluminum low in silicon. Optical microscopy, electron microscopy, and X-ray diffraction suggest that the anisotropic material contains gross areas in which submicroscopic grains of a A12O3 are oriented along radial lines drawn from the specimen surface. These lines are presumed to originate at defects in an otherwise protecting surface layer. A unique cermet is formed by the reduction of high-silica glass by molten aluminum according to the reaction: 4A1 (liquid) + 3SiO2 (glass) — 2A12O3 (a) + 3Si (solid) The free-energy change accompanying this reaction is -150 kcal at 800°C; the volume change (volume of A12O3 and silicon minus volume of SiO2) is +6 pct. The reaction product, however, contains aluminum metal as well as Al2O3 and silicon because some of the product silicon is dissolved in the aluminum bath and is replaced by aluminum in the structure. The product is a hard gray solid that retains the external dimensions of the original silica article. The system has been studied in the past, the investigations culminating in patents to George1, 2 and Saw-chuk., The former emphasize that this reaction is but one of a relatively broad class of such systems, while the latter demonstrates that a marked improvement in the gross physical properties of the cermet can be obtained by dissolving appreciable quantities of silicon in the aluminum reactant. The system has also been studied by workers at Rolls Royce Ltd.,4-6 who have patented the addition of small quantities of arsenic, antimony, bismuth, or phosphorus to the reactant bath to SO impede the reaction that glass fibers may be metal-coated by immersion in molten aluminum.

Jan 1, 1969

By W. J. Reagan

THE problem of increasing output and decreasing percentage of rejections is a vital one in the manufacture of steel of any kind. The making of basic open-hearth steel for use in rolled steel wheels, tires for locomotive and car wheels, and forgings of various kinds, is a highly specialized industry. The increase in weight of railway rolling stock of all kinds, and the high speed that the public demands of transportation facilities, make it imperative that steel for use in this class of material shall be of the highest quality obtainable. During the past few years it has been the writer's good fortune to have opportunity-to study the defects in basic open-hearth steel, and also the results obtained by various changes in open-hearth practice, on such defects. The opportunity for study and the details available are rarely found in the manufacture of steel of any kind. It seems reasonable to assume that many of the results determined here can be applied to the production of steel of other types with a decided improvement in quality, a decrease in the percentage of rejections and an increase in output. All of the material described is basic open-hearth steel with the following range of analysis: carbon, 0.50 to 0.85 per cent.; phosphorus and sulfur, 0.04 coax.; silicon, 0.15 to 0.35; manganese, 0.50 to 0.75. All of this material is bottom-cast, therefore tapping and pouring temperatures are higher than in top-cast production. Ingots used in this type of work are of standard length with varying diameters. The ingot is known as duodecagonal, or twelve-sided. The standard body length is 88 in. and the hot top length, 14 in. Fig. 1 shows a typical ingot of this type. The diameter varies from 13 to 30 in. Ingots for special forgings, which cannot be made in molds of standard size, are made in molds of various sizes and designs. These ingots are sliced cold, into blocks of various lengths, depending upon the weight of the forging to be made. Fig. 2 shows the ingot-after coming from the slicing lathe. Just sufficient metal remains between blocks to hold the ingot in one piece while it is being removed from the lathe; then steel wedges are inserted between the blocks and the blocks are broken apart. This affords abundant opportunity for inspection, as the interior of the

Jan 1, 1930

By Julian M. Avery

In its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all ecorlomy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss call be successfully attacked by increasing the over-all pressure; i.e., the "top prcssure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity. In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

By W. R. Bendy

GRINDING is a large and costly part of Portland cement manufacture. Prior to clinkering in the rotary kiln, raw materials are ground to a fineness of 80 to 90 pct passing 200 mesh. Then, after burning and cooling, the resulting clinker is ground to about 92 pct passing 325 mesh. In the cement industry the most favored method of grinding has always been by impact and attrition of a ball charge in a rotating mill. Other types of mills, in which materials are ground between die rings and rollers, or between die rings and large balls, are sometimes used for single-stage grinding and often for preliminary grinding followed by grinding in ball-type mills. Their efficiency is usually high, but maintenance and repair costs are high also, and the ball-type mill continues to be the most widely used. Together with 4 pct gypsum to retard setting time, the kiln run clinker—consisting of hard, semi-fused lumps that may have been crushed to — 1/2 in.—is ground to a Blaine surface area of 3000 sq cm per gram and about 92 pct passing 325 mesh. Approximately 32 kw-hr per ton, or 6 kw-hr per 376-1b barrel, are consumed in the grinding mills alone, not counting auxiliaries. Open Circuit Clinker Grinding: Many early clinker grinding plants employed two-stage, open circuit grinding. Comparatively short mills of large diameter, loaded with balls 4 in. and smaller, first reduced the clinker to 95 pct passing 14 mesh. Tube mills of smaller diameter and greater length, loaded with balls 11/4 in. and smaller, carried out the fine grinding operation. An early development was to assemble two or more stages of grinding in a single mill having two, three, or four compartments separated by division heads. There were difficulties in balancing the compartments, but compartment mills were popular in the 1920's because the layout was simple and there were no elevators and conveyors. Oversize Particles: Open circuit mills, whether separate ball and tube mills or compartment mills, always encountered the problem of tramp oversize in the product. A small percentage of clinker survived passage through the first grinding stage as particles—perhaps 1/16 in. diam—that were too large for the smaller balls in the following stages to reduce to —200 mesh. When the feed rate was lowered to reduce tramp oversize, there were serious losses in grinding efficiency. Many ingenious designs were perfected to incorporate perforated screen plates or wire mesh screens in the ball mills or in the first compartments of compartment mills. Their purpose was to prevent mate: rial passing out of the first stage until it was small

Jan 1, 1958

By Arthur Phillips, E. S. Bunn

During the past few years considerable interest has been shown in the study of fiber, and its effect, in wrought metals. Fiber has recently been defined as a "condition of parallelism of important lines or details in the structure."' Briefly stated, two distinct types of fiber are commonly encountered. One results from the alignment in the direction of working of constituents, more or less segregated, such as slag, oxides, carbides and dendritic formations. The second, and least understood, type is produced by working the metal below the recrystallization temperature in such a way as to develop a parallelism of the grains. This condition is readily recognized by the pronounced elongation of the grains in the direction of working. Under certain deformational treatments the grain fragments produced by cold working tend to orient in certain definite directions with respect to the axis of extension. Furthermore, even in metals that have been annealed after cold working preferred orientations may be present. It is perhaps logical to assume that such marked parallelism of structural elements would be manifested by directional properties in the metal. As a matter of fact, tests on many kinds of materials have shown differences in varying degrees. In recognition of this condition, proper design, for many purposes, places the fiber axis in such a way as to present the direction of maximum strength to the greatest applied stress. Earlier Investigations Howe2 has written at considerable length regarding the causes and practical significance of fiber in steel and wrought iron. His studies showed that wrought iron and the puddled steel sheets (materials of plastic origin) were weaker transversely than longitudinally. The transverse deficit ranged from 5 to 29 per cent. The longitudinal tests

Jan 1, 1931

By Michael A. Devane, Neil Duncan

Inclines and tunnels can extend from ground surface to considerable depths traversing a wide range of lithologies. The strata encountered may be affected by loosening and induced stresses at different locations along the route. It is suggested that Phase I of the pre- driving assessment process should include study of the geology, hydrogeology, rock material and rock mass characteristics. A rock mass disruption factor is used to express the ratio of the unconfined strength of intact rock material to the unconfined strength of in situ rock mass. It is suggested that there is a relationship between in situ (secondary) permeability values and the disruption factor, since the permeability of the rock mass is governed by parameters which influence strength. In Phase I1 of the pre-driving assessment, consideration should be given to the prediction of primary loosening which results largely from disturbances to the rock mass arising from the driving process. Also in Phase 11, preliminary assessments are made of the effects of induced stresses and of the geodurability characteristics of the rocks. In Phase 111, the mechanics of various secondary loosening pro- cesses are considered along with their relevance to estimates of stand up time and support requirements. Yield-line analysis is introduced for the study of plastic and brittle type bending deformations. Stand up time and support characteristics are also assessed. In Phase IV, the effects of induced stresses are analysed. It is suggested that even for broken rock in the Yield Zone, the rock mass disruption factor may not often increase above lo which is equivalent to an in situ permeability of 10-1 m/s.

Jan 1, 1983

By R. P. McLaughlin

In most branches of the mining industry it is a well-recognized fact that care must be taken to protect the mineral deposit from undue physical injury. It is comparatively easy to grasp this idea when the mineral is a solid and the lives of workmen depend directly upon the care with which it is removed from its natural position, but when the product is a liquid drawn up from pools several thousand feet beneath the surface of the ground through openings only a few inches in diameter, it requires some imagination to picture underground conditions and the changes which must often occur. The development of the petroleum deposits of California has been attended by numerous accidents, the results of which are readily noticed at the top of the wells and in the profit and loss accounts of the operators. Determination of the cause of these accidents has been the subject of considerable study, which naturally has fallen upon men familiar with technical methods. The greatest damage to the oil deposits of California has resulted from water finding its way into the oil-bearing sands, and it is the purpose of this paper to set forth briefly this phase of the oil industry. Much of the material here presented has previously appeared in publications issued by the California State Mining Bureau, which, under the direction of State Mineralogist Fletcher McN. Hamilton, has investigated the subject and taken steps toward improvement of conditions. The writer, having been in charge of this branch of the Bureau work, has gained considerable knowledge of existing conditions. Generally speaking, the oil-bearing formations of California are soft, unconsolidated sand beds, separated by clay strata, which are also soft. Some of the sand beds carry water instead of oil. All of the beds are more or less separated, probably being of lenticular shape. Very few of the beds in the oil fields lie flat or undisturbed over any great area. Folding and tilting are common, and faulting also occurs in some of the fields. The accumulation of oil is not confined to any single structural feature, such as the anticline, but occurs in many other structural features. Water-bearing strata occur in practically every oil field in the State. Complete data are not at hand for a comparison of the damage

Jan 1, 1916

By R. S. Handy

DOES hand-sorting of mill feed pay? The fact that the practice is so general would seem to indicate that there must be good reasons for following it; yet, to my mind, the advantage in many cases is doubtful enough to invite a thorough discussion of the subject, in an effort to determine under what conditions hand-sorting does pay. A typical sorting plant in the Coeur d'Alene district handles about 800 tons of mine-run ore per day. The material is run over a grizzly with about 4-in. opening; the oversize is crushed to about 4-in. size and joins the undersize, and the whole product is washed and screened on trommels with about 1 ½ -in. openings. The oversize from these trommels is spread on a belt and the waste and first-class ore are sorted out by hand, the residue being further crushed, and passes, together with the trommel undersize, into the mill feed bins. About 50 tons of shipping ore and 150 tons of waste are sorted out per day, leaving about 600 tons of mill feed. To sort out this material requires 20 ore sorters and five bosses and repairmen. The normal cost of hand-sorting is about 16 c. per ton of run-of-mine ore, or 65 c. per ton of material sorted out. I believe that straight crushing and milling of the run-of-mine ore, in this case, is not only cheaper, but is metallurgically moree canonical and efficient than hand-sorting followed by milling of the residue. At one of the Bunker Hill rock-houses, 1250 tons of run-of-mine ore are reduced to pass 30-mm., or about 1 ¼ -in. opening in six hours, requiring five men. The equipment and the power consumed are not greatly different from that required in a sorting plant of the same capacity, and the normal cost of thus preparing the feed for milling is under 3 c. per ton of mine product. The relative cheapness of this method as against hand-sorting is thus clearly established, the saving being about 13 c. per ton. If there is any virtue in hand-sorting, then, it must lie in the metallurgical results achieved.

Jan 4, 1918

By Cyril Smith

ALTHOUGH not of the same importance as electrical conductivity, the capacity for conducting heat is nevertheless a very important property of metals and alloys. A knowledge of thermal conductivity is of value in selecting alloys for many purposes and in the calculation of the efficiency of apparatus which is being designed. Unfortunately, the determination of thermal conductivity is extremely slow and tedious, consequently few data have been obtained. A further reason for the lack of information is that there has long been an impression that the thermal conductivity of an alloy is directly proportional to the electrical conductivity and that it can therefore be calculated from the latter. The Wiedemann-Franz-Lorenz law of constant ratio of the two conductivities holds with a considerable degree of precision for all the pure metals, but appreciable deviations occur in certain alloys-particularly those containing nickel-and it seems difficult to predict exactly what the ratio will be. Therefore direct determinations of thermal conductivity should be made whenever the results are, needed with any accuracy. This research is intended eventually to cover all the alloys of copper that are of commercial importance, including the binary alloys of copper with zinc, tin, aluminum, nickel, silicon, manganese, cadmium and phosphorus, and the ternary alloys copper-nickel-zinc, copper-nickel-silicon, copper-manganese-silicon, copper-zinc-tin, etc. Most of these alloys are customarily used in the wrought condition and therefore were tested in the form of annealed rods. A limited number of sand castings were also obtained and examined. This paper contains a complete review of all the previous work that has been done on copper alloys, and includes a detailed description of the apparatus and method of procedure used in the present research, together with the new results obtained on the copper-zinc series, which is the only one completed at the present time. Subsequent papers describing the other alloys will contain the experimental results and discussion only.

Jan 1, 1930

By S. C. Jones, J. A. Davis

This paper describes displacement mechanisms of micel-lur solution slugs, displuced by a thickened water "mobility buffer", in a glass micromodel and in consolidated Berea sandstone cores. Colored motion pictures, taken through a microscope, recorded interactions on a pore-to-pore bash in the micromodel. Production and differential pressure data from consolidated cores previously waterflooded to residua1 oil saturation revealed displacement mechani.sm.s macroscopically. Oil is displaced miscibly, while interstitia1 water is displaced immiscibly by the injected micellar. solution slug. Part of this water is dispersed and carried near the lead ing edge of the .slug, and some may remain as a residual saturation. Thickened water displaces any residual water. It also emulsifies with the. slug material, thereby displacing it. The displacement sequence forms banks of oil and water with relatively constant fractional flows, saturations, and mobilities. The mobility of oil and water flowing ahead of the .slug defines .slug viscosity required for stable displacement. Equations are presented that describe. several aspecis of the displacement flow behavior: oil breakthrough, oil cut during production of the stabilized bank, breakthrough of banked water and the resulting decreased fractional flow of oil, fluid mobilities, etc. Breakthroughs, calculated from the equations, are compared with experimental data. Slugs of micellar sollution, ranging from 1 to 5 percent PV, produced unusually high oil recoveries (up to 100 percent) in previously waterflooded consolidated cores. Investigation of the effect of mobility buffer size on oil recovery indicated that recovery is reduced in 3-in. X 4-ft cores for mobility buffer sizes .smaller than 50 percent of the pore volume. Introduction A new oil recovery process,* conceived in 1962, utilizes a slug of micellar solution' that has sufficient viscosity to avoid an unfavorable mobility ratio with respect to the oil and water it displaces. These micellar solutions are composed of hydrocarbons, water, and surfactants, and may contain electrolytes and co-surfactants. The micellar solution is displaced by a "mobility buffer". The mobility buffer is a bank of reduced-mobility fluid, preferably an aqueous polymer solution. The entire system is displaced by unthickened water. This paper describes some of the microscopic and macroscopic displacement mechanisms observed during laboratory development of the fluids for a potential field test. Microscopic phenomena were observed photographically in a specially constructed glass flow model and macroscopic data were taken from constant rate, tertiary displacements conducted in Berea sandstone cores. Qualitative Description of Micellar Solution Flooding This section qualitatively describes displacement mechanisms that occur when a slug of micellar solution is injected into a previously waterflooded core. The slug completely removes oil from the portion of core it contacts, and banks oil in the process. The oil saturation in this bank and the flowing WOR reach definite, fixed values that are determined by water and oil mobilities and slug characteristics. This zone of constant WOR and oil saturation will be called "stabilized oil bank" in the following discussion. When this stabilized bank reaches the outlet end of the core, the oil cut jumps from zero to a constant value equal to the fractional flow of oil. Saline water has little or no solubility in the slug. Because of this. the slug displaces in-place brine immiscibly. During slug injection, most of the brine is displaced ahead of the slug, some is carried along in the leading portion of the slug, and part of the brine may become immobile. The immobile, residual brine is later miscibly displaced by thickened water. Displacement of all the oil and only part of the water during slug injection results in a higher fractional flow of oil ahead of the slug than occurs when all the water is displaced after injection of thickened water is begun. The slug spontaneously emulsifies fresh (low-salt content) water. By emulsification, the slug can become infinitely diluted, and hence totally displaced, by thickened water. Fluid saturations in the core are shown schematically in Fig. 1. Parts A and B show conditions before and after the start of the thickened-water injection, respectively. Since thickened water displaces any residual brine by-

Jan 1, 1969

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By Barbara A. Thompson

A previously reported high-resolution method for the location of boron-rich areas in metallurgical and biological specimens was been adapted for general use on a routine basis. The rnetlzod utilizes neutron activation and autoradiograpizy. Alpha-particles emitted by boron nuclei upon neutron capture are recorded on a photographic emulsion. The resulting a-particle tracks show the location of boron-rich areas. Experimental techniques, interferences, and limitations of the method are discussed in detail. The method is most useful where there is marked segregation of boron. In this type of sample, the segregation can be observed when the nominal boron concentration is as low as 0.0006 pct. THE positive identification and location of boron-rich areas in metals is frequently of great interest in metallurgical work. Unequivocal identification is often difficult to make by conventional metallo-graphic methods. Recently, a method has been described which accomplishes this objective by neutron activation and autoradiography.l-3 The method can be described briefly as follows. Upon neutron capture, a -particles are emitted by boron nuclei according to the following reaction: ,Blo + n - ,a4 + 3Li7 + 2.4 mev The energy is dissipated as kinetic energy of the products. By irradiating a boron-containing sample in contact with a photographic emulsion and subsequently developing this emulsion, a-particle tracks are obtained whose location corresponds to the location of boron-rich areas in the sample. Two factors combine to make the reaction extremely specific for boron. The first is the unusually high (755 barns) cross section of boron for thermal neutron capture. The second is the higher neutron energy required to produce (n, a ) reactions in essentially all other nuclei except lithium. These two factors make the method specific for boron by six to seven orders of magnitude when a predominantly thermal neutron source such as the Brookhaven reactor is used. The reported limit of detection of this method is of the order of 0.01 pct B., The present work was originally undertaken to determine whether this limit could be lowered by use of a thinner emulsion. However, initial experiments showed that in order to use the method at all, it was necessary to reestablish the optimum experimental conditions in terms of the available irradiation facilities. It is the purpose of this paper to describe these experimental conditions in detail, to discuss the factors influencing sensitivity, and to evaluate several techniques for increasing sensitivity. EXPERIMENTAL A) Preliminary Experiments—The first measure-ments were made using samples of crystal oriented silicon steel containing various concentrations of boron. In the later experiments, samples of various high-temperature alloys such as M-252, hcoloy 901, Nichrome V, and so forth, were used. Faraggi, et al.,2 reported that the lower limit of sensitivity in this type of sample was about 0.01 pct B using nuclear emulsions of 50- u thickness. but that it should be possible to extend this limit by the use of thinner emulsions. Accordingly, we first used Kodak Auto-radiographic Stripping Film (Permeable Base) which has an emulsion thickness of only 5 µ. This was mounted on the metallographic specimens according to the technique described by Boyd.4 The emulsion remained in contact with the metal surface throughout exposure and development. Since the emulsion is transparent after development, the autoradiograph and metal surface can be viewed simultaneously and any correlation between film blackening and structure of the metal can be made directly with no problems of realignment. Because the silicon steel is readily attacked by moisture alone, it was necessary to apply a protective coating to the metal surfaces before mounting the emulsion. The coating was made extremely thin in order to absorb as few a-particles as possible. Boyd4 and Gomberg5 have discussed various plastics used for this purpose; however, none was sufficiently impermeable to prevent chemical attack of the steel during the developing process. This attack resulted in the production of gross chemical artifacts in the emulsion. It was, therefore, necessary to use the method of Wolfsberg and John6 as follows. A very thin (approximately 1 µ) coating of Plexiglas II was applied by dipping the sample in a 2 pct solution of Plexiglas II in dichloroethylene. Then, because the emulsion will not adhere to Plexiglas 11, a thin coating of Parlodion was applied in a similar manner using 2 pct Parlodion in iso-amyl acetate. No protective coating was necessary with the high-tem-

Jan 1, 1961