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By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested' and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio's waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded 'by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.' However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan'tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m'ay offer greater restriction to the production of

Jan 1, 1967

By R. S. French

THE purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,1 W. R. Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where conditions are different and the amounts of metal require necessarily longer heating times and temperatures. Study of the effect of time and temperature upon grain growth and subsequent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.125-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. TIME The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per cent hard to 0.032-in. gauge. From this piece small samples were cut ½ by 2 in., suitable for grain-size determinations. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor, A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By E. D. Gardner

The tide of increasing demand for metals turned during early 1949, with resultant lower prices. The production of the principal metals was less than in 1948. The problem of high unit costs, however, was held over from 1948. With the lower prices for metals, greater efforts are being made to reduce operating costs. The labor supply was adequate during the latter half of the year in most districts. The force has been reduced at most mines; some mines were idle during part of the year because of strikes, and others ceased operations on their own account. In the main, labor efficiency increased during the year in underground metal mines. Efforts are being made generally to improve labor relations. Green men hired in the time of the scarcity of skilled miners are becoming better trained. The supervisory personnel of most mines is cost conscious, and the planning of operations has been improved. Overhead costs are being scrutinized. The trend toward mechanization underground continued strong. Mining technology rapidly is becoming a problem of handling materials. Surface miners, underground miners and miners of metals, nonmetallics, and coal can learn much Gardner from each other. A mine, however, may become overmechanized. The capital charges against new equipment may exceed the saving in labor costs where sufficient daily tonnage is not handled.

Jan 1, 1950

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,' liquid mercury upon brass,4 and liquid mercury upon nickel.' Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.' Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962

By Arthur B. Cummins

Diatomite is a siliceous rock of sedimentary origin, which may vary in degree of consolidation, but which consists mainly of the fossilized remains of diatoms. These are microscopic algae of the order Bacillaria. Diatomite is a unique form of silica, there being nothing else found in nature or produced by the manufacturing arts, that has its characteristic physical structure. There are numerous sediments which contain some diatom residues, admixed with a substantial amount of other materials-clay, carbonates or silica. While these are classified as diatomaceous silts, shales, or mudstones, they are not properly diatomite, a designation which is restricted to material of such qualities that it is suitable for commercial uses. The terms diatomaceous earth and kieselgur are synonymous with diatomite. The expressions infusorial earth and tripolite are obsolete. Diatomaceous silica is a definition best used to distinguish the basic component of diatomite, that is, the substance of the silica shell itself and is the major constituent of beneficiated diatomite or processed diatomaceous products. Some highly indurated materials, such as cherty shale, porcelanite, and opaline cherts which have resulted from diagenetic changes cannot be considered as diatomite although they may have been derived therefrom. On the other hand, diatomaceous oozes or loose sediments consisting mainly of diatom residues with or without much organic matter are source materials in process of becoming diatomite. Composition and Properties Pure diatomite is composed of opaline or hydrous silica, with small amounts of associated inorganic components-alumina, iron, alkaline earths, alkali metals, and minor constituents, all of which may occur in solid solution or as an essential part of the opal complex. Crude diatomite on the other hand may contain variable amounts of organic matter and soluble salts, and the usual contaminants of sedimentary formations-particles of rockforming minerals, sand, clay, or carbonates. As occurring in nature, diatomite contains an unusual amount of free water, which may vary from 10 to 60 pct or more. Diatomite, in the dry deposits which are characteristic of most of the important world deposits, occurs as a lightweight, comparatively light colored, "chalklike" material. The apparent density (dry basis) in situ varies from 20 to 40 lb per cu ft. The structure may be either massive or finely stratified. The earth is highly porous, usually soft and easily friable. It is nonreactive with acids and may be tentatively identified by the above characterizations. Confirmation is by microscopic examination which readily reveals the nature of the material. In deposits which contain organic matter the appearance of the material is totally different. The color may vary from light tan or gray to brown, greenish or nearly black. There is frequently difficulty in distinguishing it in the field from peatlike materials, but the difference is readily apparent after calcination. Powdered diatomite or diatomite products have an apparent density (loose weight) of 5 to 16 lb per cu ft, wet densities of 10 to 30 lb per cu ft, specific gravities 1.9 to 2.35, index of refraction 1.42 to 1.48. Diatomite is essentially micro-amorphous, but does show some tendency toward orientation in structure after a cristobalite pattern. Amorphous silica has been considered as a random association of cristobalite crystallites, the size of which are only slightly larger than a unit cell.20 The prop-

Jan 1, 1960

By J. J. Kanter

There has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-temperature steels" are meant those specifically designed for service at elevated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service. Uses of Silicon Next to oxygen, silicon is the most widely distributed and abundant of the earth's substances. Although classed as a nonmetal, it is highly important in the metallurgy of all steels, having been used for years as an efficient and economical degasifier and deoxidizer. Silicon is added to various steels in the form of ferrosilicon, generally at the end of the heat so as to avoid oxidation losses. With acid steels it is added in the furnace (also in the ladle) and generally with basic steels is added in the ladle, so as to avoid reaction with the basic lining through high-temperature acidic reaction with silica, which may be formed by oxidation of the silicon alloy. Several grades of ferrosilicon are available, containing, respectively, 15, 50, 75 and 90 per cent Si. By far the largest tonnage produced is the 50 per cent grade although the 75 and 90 per cent ferro-silicons are used as ladle and furnace additions in the manufacture of steels of high silicon content. The introduction of silicon into steel as an alloying element is well known in connection with high-yield-strength constructional steel for bridges, ships, car construction, etc., and it is also well known as an alloy-

Jan 1, 1938

By J. J. Kanter

There has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-temperature steels" are meant those specifically designed for service at elevated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service. Uses of Silicon Next to oxygen, silicon is the most widely distributed and abundant of the earth's substances. Although classed as a nonmetal, it is highly important in the metallurgy of all steels, having been used for years as an efficient and economical degasifier and deoxidizer. Silicon is added to various steels in the form of ferrosilicon, generally at the end of the heat so as to avoid oxidation losses. With acid steels it is added in the furnace (also in the ladle) and generally with basic steels is added in the ladle, so as to avoid reaction with the basic lining through high-temperature acidic reaction with silica, which may be formed by oxidation of the silicon alloy. Several grades of ferrosilicon are available, containing, respectively, 15, 50, 75 and 90 per cent Si. By far the largest tonnage produced is the 50 per cent grade although the 75 and 90 per cent ferro-silicons are used as ladle and furnace additions in the manufacture of steels of high silicon content. The introduction of silicon into steel as an alloying element is well known in connection with high-yield-strength constructional steel for bridges, ships, car construction, etc., and it is also well known as an alloy-

Jan 1, 1938

Jan 1, 1922

By Turno De Michelis

The Porto Marghera plant was erected in 1936 for the production of 10,000 tons of electrolytic zinc annually. Since then it has been continuously enlarged until annual production of the metal reached 40,000 tons in 1969. At the same time the processing cycle was modified bringing it up to date with modern techniques, and was completed by installations for the recovery of by-products in the minerals treated and subsequent processing of the base metal. 90% of the zinc produced is of 99.993% purity . At present the plant comprises, first of all, the zinc blende desulphuration department which has a single modern fluid bed furnace capable of processing 220 - 250 tons of dry crude mineral daily; it is connected to the sulphuric acid plant with its three catalysis sections each capable of producing 60-70 tons of sul9huri.c acid monohydrate daily. The roasted blende is conveyed pneumatically to plants for leaching of the zinc and purification of the resulting solution. During recent years this department has been completely transformed from the discontinuous cycle, for which it was built, to the continuous cycle, paying great attention to

Jan 1, 1970

By D. A. Hinckfuss

The large and compact but simple Bougainville Copper Limited flotation circuit has been in operation for 3-1/2 years. Discussion of problem areas encountered since start-up and remedies that have been implemented or proposed, form the main basis of this paper. Full current operational data is also provided.

Jan 1, 1976

By S. F. Shaw

IN 1913, the Tiro General mine, at Charcas, S.L.P., Mexico, which had been making from 125 to 150 gal. of water per min., was allowed to become flooded, after all the pumps had been removed, and in 1918 the problem of unwatering it came up for solution. There are two vertical shafts, the Tiro General, 1390 ft., and the San Fernando, 1225 ft. in depth, with five connecting levels between them. The San Fernando shaft had been partly retimbered, while the Tiro General had been newly timbered from the collar to, 1090 ft. in depth. It had been possible to place guides in only one compartment of the Tiro General, from the collar to the seventh or 850-ft. level, to which it was necessary to lower the water before station pumps could be installed. Soundings indicated that compartments in the Tiro General were open to 1082 and 428 ft., and in the San Fernando shaft to 471, 488, and 586 ft. The water had risen to a point 140 ft. below the collar of the Tiro General shaft. PUMPING EQUIPMENT The steam plant at the Tiro General shaft includes one 300-hp., one 150-hp. and one 100-hp. Erie City water-tube boiler, and two 160-hp. Heine water-tube boilers. All but one of these boilers were supposed to be in good shape, but it was soon discovered that six years of idleness in a climate that is foggy for several months of the year had left them in poor condition. The compressed-air plant comprises one Nordberg cross-compound compressor with piston displacement of approximately 2500 cu. ft. of free air compressed to 96 lb. per sq. in.; and another Nordberg cross-compound with piston displacement of 1235 cu. ft. of free air, to the same pressure.

Jan 2, 1920

By Floyd Kelley

THE literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke's iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be util-ized to the fullest extent there must be a thorough investigation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibrium produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizing1 which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure.

Jan 1, 1928

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep¬resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geological Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is, one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,' detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By Waldemar Lindgren, Clyde P. Ross

To the miner, as well as to the geologist, the eastern part of Cuba is a most interesting region. Here we find, in contrast to the moderate relief predominating elsewhere in the island, an imposing mountain range, the Sierra Maestra, extending east and west parallel to the coast, its precipitous front facing the blue Caribbean Sea. In a geological sense this range is largely an unknown land, the only well-explored region being that in the vicinity of Santiago. The range also contains the most important mineral deposits of the island. They comprise, first, a series of iron deposits yielding a partly hematitized magnetite with low content of phosphorus; second, a remarkable copper-bearing vein at El Cobre; and third, various manganese deposits. Probably more deposits will be found, for the larger and western part of the range is as yet little explored and its slopes are covered by a thick tropical jungle. The following notes are based on a short visit by the senior author in January and February of 1914 to the mines at Daiquiri, El Cobre, and Mayari. For many courtesies and great assistance he is deeply obliged to Charles F. Rand, President of the Spanish-American Iron CO.; to George W. Pfeiffer, General Manager, and to the several members of his staff. Geological Features of the Sierra Maestra For our knowledge of the geology of the Sierra Maestra we are indebted to reconnaissance work by Fernandez de Castro, R. T. Hill, Mr. C. Hayes, T. W. Vaughan, and A. C. Spencer. The summary by the latter three geologists furnishes the best guide to the region.' The range is undoubtedly outlined by a great east-west dislocation. Its southern slope drops abruptly to the sea, while on the north side a much gentler declivity leads down to the rolling plateau of Tertiary limestone which occupies much of the adjacent part of the island. Viewed

Jan 1, 1916

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By H. I. Aaronson

The nucleation of pearlite at proeutectoid ferrite is inhibited, to an increasing extent, at the following locations: At twin boundary-nucleated ferrite, between closely spaced ferrite sideplates, and at intragranular plates. These effects are discussed in terms of the influence of transformation strain energies and of the interfacial free energy of austen-ite:ferrite boundaries on the rate of pearlite nucleation. The growth of pearlite into the interiors of austenite grains from the region of the grain boundaries is markedly restricted when low reaction temperatures and large austenite grain sizes permit the development of interlocking networks of intragranular ferrite plates. PREVIOUS investigators have made extensive studies of the interactions which occur between the proeutectoid ferrite and the pearlite reactions from the viewpoint of the mechanisms through which pearlite interferes with the nucleation and growth of proeutectoid ferrite.1-3 In the present investigation, the processes through which proeutectoid ferrite (hereafter termed simply "ferrite") can reduce the rate of formation of pearlite have been explored in some detail. A steel with a relatively low carbon content, in which the ferrite reaction can compete successfully with the pearlite reaction over a wide range of reaction temperature, and exceptionally coarse-grained specimens, which further emphasize the role of the ferrite reaction, have been employed for most of this work. A brief examination also has been made, however, of the effects of smaller austenite grain sizes upon these processes. Experimental Procedure The steel employed had the following composition: 0.29 pet C, 0.76 pet Mn, 0.25 pet si, 0,007 pet S, and 0.005 pct P. This alloy was homogenized for 48 hr at 1250°C. The investigation was performed

Jan 1, 1959

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.' A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

By Marshall D. Himes

The Pima mine, Pima County, Ariz., a 53,500-tpd copper mine, is located 17 miles south of Tucson, Ariz. The mine is in a sequence of Paleozoic and Mesozoic sediments striking east-north-east and dipping southeasterly. These sediments are intruded by a Tertiary quartz monzonite porphyry. The Paleozoic Permian (?) dolomites, limestones, and sandstones have been altered to calc-silicate skarn, marble, and quartzite. The overlying Mesozoic Triassic (?) clastic sediments have undergone some recrystallization and hydrothermal alteration. The clastic metasediments are divided into three distinct lithologic units: lithic arenite, arkose, and interbedded and overlying black argillite. Three types of hydrothermal alteration in the clastic rocks are propylitic alteration (epidote, chlorite, and quartz, with or without sericite), quartz-sericite alteration, and potassic alteration (K-feldspar, quartz, and sericite, with or without chlorite and calcite). The porphyry has undergone potassic alteration. Dominant structures are an east-west postmineral fault in the western part of the pit, and strong low angle faulting and shearing which truncates the ore body at depth. The two joint sets, one parallel to bedding and the other at right angles to bedding are prominent in the mine. Faulting is in two dominant directions, one striking northwest, dipping northeast, and the other striking northeast, dipping northwest. Economic mineralization is prediminantly disseminated pyrite and chalcopyrite, and molybdenite-quartz veinlets. There are less important amounts of magnetite, hematite, sphalerite, galena, tennantite, and bornite. Mineralization is believed to be both structurally and chemically controlled.

Jan 1, 1974

By F. M. Yans, A. D. Donaldson, A. R. Kaufmann

Beryllium was mixed by powder. metallurgical techniques with copper, nickel, iron, and chromium, respectively, to form beryllium -rich binary alloys which Mere then extyuded and rolled transtverse to the extrusion direction. The effect of each alloying element was determined by tensile testing. In solid solution, small amounts of iron and nickel had an embrittling effect, while copper in solution increased the strength but had no effect on ductility. The effect of chromium was complicated and not readily explainable. Observations concerning the planes and modes of fracture were made. BERYLLIUM possesses some very attractive properties for general design applications, especially its strength to weight ratio which is approximately twice that of aluminum and three times that of stainless steel. Equally significant, however, is its combination of high moduli , high strength (approximately 70,000 psi tension and 40,000 psi shear), and low density (0.0658 Ib per in.3), which has made it a potentially important structural material for use in high-speed aircraft and missiles. The main attractions of beryllium are most marked when compared to other constructional alloys now in use. For example, while its density is approximateiy that of magnesium, its modulus of elasticity is approximately seven times that of magnesium, three times that of titanium, four times that of aluminum, and 1 1/3 times that of steel. Furthermore, its relatively high strength and high melting temperature permit design for service temperatures to about 1100°F. It is felt by the aircraft industry in general,' that the high cost of beryllium can easily be amortized by the savings in fuel costs, and increases in aircraft payload and range. The only factor which has prevented the use of the metal in structural applications is its lack of sufficient ductility. It is this property that has retarded the development and utilization of beryllium. Beryllium's modes of deformation, Fig. 1 indicate that the main fracture planes at room temperature in a randomly oriented sample are the (0001) basal planes; the (1150) prism planes are the planes of secondary fracture.' Klein, Macres, Woodard, and Greenspan3 obtained elongations of up to 40 pct in beryllium sheet rolled above 700°C when the (0001) basal planes were oriented parallel to the plane of the sheet (see Fig. 2).

Jan 1, 1962