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Jan 1, 1920

By George Krauss, M. Cohen

The reverse martensitic transfomzation (i.e., the conversion of martensite to austenite on heating) was investigated in Fe-Ni alloys containing 30.5 to 33.5 wt pct Ni. The reversed austenite was found to be sufficiently distorted to exhibit marked differences in mechanical properties and to undergo recovery and re crystallization on further heating. In particular, the yield strength of the reversed austenite was as much as 2.5 times higher than that of the virgin austenite: with five cycles of the direct and reverse martensitic transformation, the yield strength was 2.6 times higher. There was an accompanying decrease in strain-hardening capacity and in stable ductility or uniform elongation. The recrystallization was observed to follow sigmoidal kinetics, but was characterized by an abnormal1y large temperature dependence which was evidently due to carbon segregation at the migrating grain boundaries. Upon recrystallization, the strength Properties reverted to those of the virgin austenite, but the ductility did not fully recover until the annealing temperature was further raised to dissipate the carbon segregation at the grain boundaries. The transformation of reversed austenite to produce second-generation martensite resulted in an unusually imperfect structure, thereby leaditg to additional strengthening. Horlleuer, the martensitic phase was much less responsive in this respect than was the austenite. MOST martensitic transformations are capable of undergoing a reverse transformation back to the austenitic phase on heating.&apos; This reaction, like the direct transformation to martensite on cooling, is usually athermal. In analogy with the Ms andMf temperatures for the martensitic transformation (where M, > Mf), the reverse transformation is characterized by the As andAf temperatures (where As<Af). It is well-known that the finish (Af) of the martensite-to-austenite reaction on heating may occur at a temperature where austenite is not stable relative to other phases in the equilibrium diagram.&apos; Reverse martensitic transformations have been found to influence the properties of the parent austenitic phase in a number of ferrous alloys. The austenite thus produced after one or more reversals is significantly altered in strength, microstruc-ture, diffusivity, and annealing characteristics compared to well-annealed, virgin austenite. The first detailed observations of such phenomena were made by Wasserman3 on an Fe-30 wt pct alloy. He found that the reversed austenite (i.e., austenite formed by the reverse martensitic transformation) was much stronger than the original austenite, and the second-generation martensite (i.e., martensite produced from the reversed austenite) was somewhat stronger than the first-generation martensite. On heating the reversed austenite, recrystallization occurred in a manner similar to that of a cold-worked metal; the Laue spots sharpened and the strength decreased.4 In recent years, Russian workers have shown considerable interest in these reverse martensitic transformations. Most of such investigations5-10 have been concerned with the stabilization of reversed austenite relative to subsequent martensitic transformation, and because of its unusual nature, this phenomenon will be discussed in detail elsewhere." On the other hand, the annealing behavior of reversed austenite and the attendant variation in properties have received little attention beyond the experiments of Wasserman.3,4 Gridnev eta1.,8 in one of the few such studies. followed the hardness change of reversed austenite as a function of time at three annealing temperatures. The marked strengthening of austenite achieved by the reverse martensitic transformation has been referred to as "transformation strengthening" by Wasserman3,4 and as "phase hardening" by Malyshev et a1.7,9,10 to differentiate it from hardening produced by cold working. Both groups of investigators noted that further strengthening of the austenite could be attained by repeated or cyclic transformations, but the first cycle resulted in the most pronounced effect. Evidence of the altered microstructure of reversed austenite has been reported by Maximova and Nikonorova6 and by Edmonson and KO.12 The former found that reversed austenite was much more sensitive to etching than the original austenite, and the latter authors observed a (&apos;ghost" structure resembling martensite in certain areas of the reversed austenite. Enhancement of the self-diffusion rate in reversed

Jan 1, 1962

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.&apos; In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By I. R. Kramer, H. Shen, S. E. Podlaseck

The tensile and creep properties of aluminum in vacuum have been investigated. It was found that the general effect of a vacuum environment was to reduce the rate of work hardening. Results obtained from creep tests showed that lowering the test pressure from 2 x 10-4 to 10-7 torr produced a decrease in the activation energy as much as 500 cal per mole. An attempt is made to explain these effects in terms of how the surface-stress field of a specimen may be affected by a vacuum environment during plastic deformation. In a previous paper,&apos; the results were reported of some of our early work on the effect of vacuum environment on the stress-strain curve of aluminum single crystals. This effort has been extended to the studies of the tensile and creep properties in vacuum as a function of various metallurgical parameters. Some of the recent surface-effect studies2&apos;3 have revealed that a region of high dislocation density, the so-called "debris" layer, is formed near the surface of the specimen as a result of plastic deformation. This layer acts as a surface barrier to oppose dislocation movement. The strength of this barrier depends on the surface condition such as oxidation or surface removal. Experimental results obtained from surface-removal work2, 3 indicate that such a surface barrier, which may be characterized by a stress field, affects the applied stress and the rate of work hardening. In the case of aluminum, this stress field was found to be directly proportional to the strain and the strain rate; however, the slope of this curve is independent of orientation of the crystal and may be altered by using different surface treatment. Since the escape of dislocations may be retarded by the presence of an oxide on the surface of a specimen, it is expected that a change in the rate of oxidation in vacuum will affect the process of dislocation accumulation in the debris layer. Consequently, it also affects the plastic behavior of a metal. This paper reports the changes in some of the creep and tensile properties of aluminum in vacuum and discussions of the observed effects in terms of the concept of the "debris" layer. EXPERIMENTAL PROCEDURE Tensile Tests. A sketch of the tensile apparatus is given in Fig. 1. This apparatus was contained in a bell jar (14 in. diam by 24 in. high) connected to a 10-in. vacuum system. The load was applied to the specimen by means of a gear train which was driven by a magnetic clutch located outside the vacuum chamber. The specimen, held by a pair of square shoulder grips, was attached to the load cell at the top and the drive gear at the bottom. A displacement transducer was placed between the two grips as shown in the figure to measure the elongation. Signals of elongation and load were amplified and recorded on an X-Y recorder. The system was capable of detecting loads as small as 0.025 lb and displacements of 0.0002 in. Shoulder-grip specimens of aluminum single crystals, having a nominal square cross section of 1/8 by 1/8 in. and a 3-1/2-in, gage length, were grown by the Bridgeman techniques. The original purity was 99.997 pet. The orientations of the crystals investigated are shown in Fig. 4(a). The crystals were annealed at 600°C for 2-1/2 hr, electropolished, and placed in the vacuum test chamber without any delay. All the crystals were deformed at a strain rate of 4 x 10-5 sec-1 at 24o ± 3°C. A study was made to find whether a chemically passive surface film would give the same effect as a vacuum environment. Specimens of aluminum 1100 (0.187 in. diam with a grain size of 0.1 mm)

Jan 1, 1965

By Elmars Ence, Harold Margolin

The titanium-aluminum system has been investigated in the composition region 0 to 34 pct Al in the temperature range 800" to 1450°C. The phases encountered in this region were: a,ß, TiAl3, The reactions observed are as follows: 13 ; L - 6T. A1, 0 (15 pct Al) + 6 (18 pct Al) - yTi Al (16.5 pct Al) at -1170°C andP (7 pctpct Al) + y (9.2 pet Al) - ah(9 pct Al) at - 1060°C. A eutectoid reaction: y — a +d belm 700°C is postulated. THE Ti-A1 system has been the sub.ect of a number of investigations. Several of these1-3 have indicated extensive solubility of A1 in both a and ß titanium. Ence and Margolin, as a result of work on the Ti-A1-0 system:&apos;5 have shown that the a solubility ofalumi-num is considerably restricted, and found that a compound, Ti2A1 existed in the region formerly designated as Q a This structure was identified as hexagonal with c/a = 0.803. Pietrokowsky confirmed the existence of this phase7 and pointed out that the structure was isomorphous with Ti3Sn.8 Although the existence of Ti,A1 has been confirmed by others,9-12 there has been considerable disagreement regarding the composition and mode of formation. A detailed reinvestigation of the Ti-A1 system has been published by Sagel et al.13 The tentative diagram indicated two phases, a, and e, occurring in the former all a region. The a, phase has the same structure as Ti2A1 and was indicated as having a broad region of solubility. Epsilon, a tetragonal phase, was shown to form within the a, solubility region. AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed. The present study was conducted in an attempt to clarify prevailing uncertainties. EXPERIMENTAL PROCEDURE Alloy Preparation—Alloys were prepared from iodide titanium (99.9 pct Ti with less than 0.01 pct Zr) or Bureau of Mines electrolytic titanium (BHN-73) and high purity aluminum (99.99 pct). Alloys were arc-melted in argon or helium atmosphere as 15-g buttons in the composition range up to 34 pct Al. Depending on need, alloys were made in increments varying from 0.25 to 2 pct Al. Up to five 15-g buttons of some compositions were made. Weight losses during melting did not exceed about 1 pct of the charge and chemical analysis revealed that both titanium and aluminum were evaporated. In general, nominal and analyzed compositions agreed within 0.5 pct and therefore nominal compositions were used in plotting the data. Unavoidably, some overlap of composition occurred, particularly where small increments of A1 were used. The small increments were primarily used to obtain alloys which would fall into the narrow a -, r region and this purpose was achieved. In general, the data obtained from Bureau of Mines base titanium and iodide titanium alloys were in agreement. Forging—Both as-cast and forged samples were employed. Samples were heated for hand forging by an oxygen-hydrogen torch to the region 1200" to 1300°C. A titanium anvil and cover plate were used to prevent any iron pick-up and consequent formation of a low melting point compound. Frequent reheating kept the temperature in the desired range. Under these conditions, alloys containing up to 15.5 pct could be successfully forged. To check on the depth of contamination, forged alloys were heated slightlybelow the ß transformation temperature. Metal was removed to a depth below the contaminated surface so revealed, and the subsequent results obtained from these samples agreed closely with those secured from as-cast material. Heat Treatment—Prior to heat treatment, all alloys were vacuum annealed to remove hydrogen. Samples

Jan 1, 1962

By A. Taylor

NICKEL-RICH alloys hardened with small additions of titanium and aluminum and centered around that region of face-centered-cubic primary solid solution, 7, where the atomic ratio of nickel chromium is about 3 to 1, form an important series of high temperature materials because of their resistance to oxidation, high temperature strength, and excellent creep characteristics at elevated temperatures.&apos; With suitable heat treatment it is possible to precipitate a phase based on the ordered face-centered-cubic y&apos; phase, Ni,,Al, from the randomly ordered nickel-rich y face-centered-cubic primary solid solution. By adjusting the ratio of aluminum to titanium the precipitation of needles of the hexagonal intermetallic compound n-NiaTi may be effected. In the present investigation, the main interest was focused on the interrelationships among the y, y, and 7 phases. By using alloying elements of high purity and a suitable melting technique the presence of carbides and nitrides could be completely obviated, although it is realized that their presence is probably essential in alloys of commercial importance. As a preliminary to the study of the Ni-Cr-Ti-A1 system, it was necessary to establish the constitutional diagrams of the three contiguous systems, Ni-Cr-Al, Ni-Ti-Al, and Ni-Cr-Ti, which together form the nickel-rich corner of the Ni-Cr-Ti-A1 quaternary tetrahedron. Accounts of this work on the ternary systems have already been published by the author. A preliminary disclosure of the author&apos;s investigations on the ternary and quaternary systems has been made by Hignett2 and has since stimulated work in the same field by Nordheim and Grant." Before the detailed account of the quaternary system, a brief description will be given of the three contiguous ternary diagrams on which it is ultimately founded. Ni-Cr-Ti System The 750° and 1000°C temperature isothermals of the Ni-Cr-Ti system as determined by Taylor and Floyd&apos; are shown in Figs. 1 and 2. The single phase fields of greatest interest are occupied by the extensive face-centered-cubic y primary solid solution of chromium and titanium in nickel, and the close-packed-hexagonal Daltonide, n-Ni3Ti, from which tie-lines radiate across the very wide y+n two-phase field. The chromium-rich primary solid solution is represented by a. As may be seen from the diagrams, the extent of the y phase field increases quite appreciably as the temperature is raised from 750" to 1000°C. Isoparametric lines for the y phase are shown in Fig. 1. They are interesting in that they are almost parallel to the y/r+n boundary. Thus the determination of the tie-line directions is entirely dependent on the exact stoichiometry of composition of the 7 phase. Ni-Ti-Al System The 750°C isothermal section of the nickel-rich portion of the system Ni-Ti-A1 as determined by Taylor and Floyd is shown in Fig. 3.&apos; The regions of greatest interest are the extensive y primary solid solution of titanium and aluminum in nickel, the y&apos; Berthollide phase field based on the ordered face-centered-cubic structure of Ni3Al, and the hexagonal Daltonide phase, n-Ni3Ti. As may be seen from Figs. 3 and 4 the area occupied by the y phase is substantially the same at 750°C as at 1000°C, but the area of the 7 phase is considerably greater at the higher temperature. The tie-lines radiate from n-Ni3Ti across the y+v and y&apos; + v two-phase fields and are evenly distributed

Jan 1, 1957

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman&apos; and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964

By R. E. Zimmerman, Michael Sokaski, E. R. Palowitch, M. R. Geer, H. F. Yancey, W. Deurbrouck, S. C. Sun

PART 1: DENSE MEDIUM SEPARATION by M. SOKASKI, M. R. GEER and H. F. YANCEY INTRODUCTION In the early days of coarse-coal treatment by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken :he loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Netherlands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War 11 in the laboratory of the Dutch State Mines under the direction of M. G. Driessen. A 15-ton-per-hour pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of Fuel in London. In April 1945,2 operation of this pilot plant was observed by one of the authors, who was so impressed with the potential of the cyclone process that, on his return to the United States, a research program on the cyclone was started by the Bureau of Mines immediately. This work led to an AIME paper in 1946 in which the first details of cyclone operation on American coals was made available. Commercial adoption of the cyclone proceeded in Europe, initially in the Netherlands, Germany, and France. In the United States, where coal is less costly and most of the coals are so easy to clean they respond well to simpler cleaning systems, the first cyclone plant was not built until 1961.3 As of the spring of 1967, a total of 31 commercial cy- clone plants had been installed or were under construction in the United States; this does not include eight Dynawhirlpool plants. The capacity of the cyclone plants ranges from 50 to 1300 tons per hour and totals 6600. THEORY Before discussing the theory of a dense medium cyclone, a brief description may be helpful to some readers who are not familiar with its basic operation. In a typical dense-medium cyclone, illustrated in figure 10-1, the mixture of medium and raw coal enters tangentially near the top of the cylindrical section, thus forming a strong vertical flow. The refuse moves along the wall of the cyclone and is discharged through the under- flow orifice. The washed coal moves toward the longitudinal axis of the cyclone and passes through the vortex finder to the overflow chamber.

Jan 1, 1968

By Frederic Carter

THERE have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it had not been known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there had been noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals had been meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20. lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or, flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

Jan 1, 1928

By Paul A. Taylor

MUCH information concerning pegmatites which was thought to be true a few years ago has been proved false, and what is now actually known about some pegmatites is not true of many others. The erratic and seemingly unpredictable structure and variable composition of this class of mineral deposits has been widely emphasized. Even parts of the same pegmatite body exhibit marked differences in texture, mineral composition, width, and attitude. Constructive geological thinking in respect to pegmatites now aims to establish general laws rather than to stress the confusing diversity of features having no special economic significance. Substantial progress has been made in classifying different types of these deposits according to general features, internal structure, mineralogy, and origin. In some cases it has even been possible to block out tonnage reserves in advance of mining. It is still easy, however, to make highly erroneous predictions after a preliminary examination of a pegmatite prospect. Pegmatites are important to the economic well being of the country and to its military security. They furnish virtually all the feldspar, strategic mica, beryl, columbium, tantalum, and caesium utilized in the United States, as well as sundry other minerals and significant amounts of lithium and rare earth minerals and gems. With the exception of vermiculite, occasional ilmenite-rutile, and perhaps soda-lime feldspar and garnet deposits, basic pegmatites are of little economic importance. Consequently in this paper, as in common parlance, the term pegmatite generally relates to coarsegrained acidic rocks or what is aptly called giant granite. Available data indicating the size and importance of the production and trade in specified pegmatite minerals are summarized in Table I. Geological Features Much of the latest thinking on the economic geology of pegmatites is now available in a 115-page monograph&apos; by a group of experts who participated with geologists of the Federal Geological Survey in the widespread wartime investigations. Doubtless the most significant feature of the monograph is indicated by the title, The Internal Structure of Pegmatites, but it also contains a vast amount of other new information and includes the assimilated concepts of many earlier writers, whose works are given in a comprehensive list of references. The shape, size, attitude, and continuity of many pegmatite bodies is controlled by the structure of the older rocks in which they occur. If the older rocks are easily penetrated, e.g., biotite schist, most of the pegmatites in a given district will be found outside the parent granite mass as exterior pegmatites. Marginal pegmatites are more prevalent if the older rocks are massive, unsheared, and sparingly jointed. Networks of pegmatites are abundant in highly-jointed rocks. In strongly foliated schists the bodies are usually lenticular, whereas in highly-folded areas they assume tear drop, pipe or pod-like, bow-shaped, or sinuous forms. Jahns2 recognizes five major shape classes: l—dikes, sills, pipes, and elongate pods; 2— dikes, sills, pipes, and pods with bends, protuberances, or other irregularities; 3-—trough-or scoop-shaped bodies with or without complicating branches; 4—bodies with the form of an inverted trough or scoop; and 5—other bodies, including combinations of the above and miscellaneous shapes. Many pegmatite deposits are scarcely big enough to be recognizable as such. Most of them, in fact, are small tabular deposits less than 4 in. wide and usually without economic concentrations of minerals. On the other hand, some pegmatites are more than a mile long and over 500 ft wide. The ratios of length to breadth range from 1 : 1 to 1 : 100. Although the vertical dimension bears no invariable relationship to strike length, tabular deposits or large lenses are often symmetrical enough to show nearly as much continuity down dip as in their horizontal extension, and some pipes or pods are amazingly persistent in the vertical plane. Small pegmatites often string along a fairly definite trend line; in a given district major bodies may lie roughly parallel, and where only a few of them do not, the erratically disposed bodies generally differ in composition from those conforming to the regular pattern. This does not apply, however, in all districts. Characteristically, pegmatite veins pinch and swell or split into branches. When they pinch out entirely it is often possible to find a new body by prospecting the extension of the strike or dip, but the chances of finding a hidden deposit are ordinarily too uncertain to justify much subsurface prospecting. Diamond drilling may yield valuable information as to the continuity of known deposits whose upper portions are well-exposed. Some deposits, in fact, can be proved up for hundreds of feet by surface trenching and then intersected by drill holes at various depths like any other vein-like deposit. Others twist and branch, apparently defying all efforts to explore them short of actual mining.

Jan 1, 1954

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890&apos; and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,&apos; the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

Jan 1, 1928

By Robert C. Paddock

INTRODUCTION A way of producing 3,000 tpd from the El Mochito Mine was needed. Of this production, 2,000 tpd must come from the San Juan orebody. The original sub-level stoping method did not give satisfactory results due to ground instability, and the highly irregular ore/waste contacts encountered . The experience gained from the initial system helped guide research into the ground instability problem. Results from this work, combined with knowledge gained about the orebcdy configuration, defined constraints that were previously not fully appreciated. These constraints, and others, combined with objectives, were considered together to develop a new mining method. No single technique was found to be suitable, so a hybrid mining system was developed. A combination of ramping, cut and fill, and vertical crater retreat, with an option to use top heading and benching was developed. To complement the mining system, the type of equipment needed was decided upoun. Also, to support the mining system at this expanded rate of product ion, major modifications of existing infrastructure were required. THE EL MOCHITO MINE The El Mochito Mine, of Rosario Resources Corporation, has been in continuous product ion since 198. The mine began operations in April of that yeas at a rate of 100 tpd. The reserves in 198 were 100,000 tons of silver ore assayed at 1,250 grams per tonne. As of the end of 1979, the El Mochito orebodies have produced over 5.6 million tonnes of ore averaging 516 grams per tonne silver, 6.8 lead, and 7.8% zinc. Present ore reserves are about 7.9 million tonnes, averaging 138 grams per tonne silver, 4.6% lead, and 8.7% zinc, with minor quantities of copper, cadmium and gold. An expansion plan to increase mill production two fold to 2,500 tonnes per day is underway. This expansion will require the mine to produce 3,000 tpd. The mine consists of numerous orebodies, all of which have been mined to a certain extent. Of all the orebodies, the San Juan contains 8% of known reserves. This amounts to about 6.7 million tonnes. The significance of the San Juan orebody to the future life of the El Mochito Mine is obvious. If the required mine production of 3,000 tpd is to be sustained, the San Juan must be the source of the majority of that production. Due to the mineability and overall logistics concerned with the other orebodies, the San Juan must be able to reach and maintain a production rate of 2,000 tpd by 1982. GEOLOGY OF THE SAN JUAN OREBODY The El Mochito Mine is a classic example of a chimney replacement deposit in limestone. Similar deposits axe found in Mexico, at the Naica, Providencia, and Santa Eulia Mines. The El Mochito Mine is located at the south- western end of the Sula Valley on the western edge of the Honduras Depression in the Central Cordillera and Central Highlands of Honduras in a setting of Mesozoic sediments. The orebodies occur in a structural basin developed between NNE trending normal faults and apparently hinged on the south end. Topographically, the Mochito Basin lies between the uplifted Santa Barbara mountain in the west and the Palmer Ridge on the east. The San Juan orebody occurs near the intersection of the NE trending San Juan fault and the ENE trending Porvenir fault. The downward continuation of the orebody is controlled by the westward rake of these NW and N dipping structures. The discovery of the San Juan orebody is attributed to analysis of structural evidence of known ore deposits by in-company geologists. The composition of the San Juan orebody is primarily garnet skarn, with local concentrations of hedenbergite and magnetite. The economically important sulfide mineralization consists of (in decreasing abundance), sphalerite , galena, pyrrhotite , and chalcopyrite. There is some indication that a Cu-Ag mineral such as tetrahedrite may also be present. The skarns were formed by replacement of the original limestone by hydrothermal water migrating upward roughly along the intersection between the Porvenir fault system and the San Juan fault system. Textural evidence suggests that the orebody is a composite of several pulses of hydrothermal activity which would explain, in pat, the great irregularity of the contacts and the large horizontal variation in mineralogy. A general pattern of skarn types can be seen in the orebody, partially accounting for the observed lateral variation in grades. This zonation is very generalized, and one or more zones may be missing in any given locality. The orebody is almost invaxiably surrounded by a 2 cm to 25 cm zone of bustamite skaxn with low values. The border skarn is usually

Jan 1, 1981

Jan 1, 1930

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,&apos;-!&apos; other investigators have encountered difficulty with the method."&apos;. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By William G. Pariseau, H. Douglas Dahl

Recent subsidence legislation indicates that mining engineers would be welt advised to be able to predict and control surface damage caused by mine subsidence. To date, such an ability is practically nonexistent. Model analysis is suggested as one of the alternative paths available which might yield fruitful results. Similitude requirements developed for a self-loaded body in static or quasi-static equilibrium indicate that complete similitude without centrifuging is an impracticability. However, a pilot experimental study which used a simplifying assumption to correctly model mine subsidence has produced results in qualitative agreement with field observations. The purpose of this paper is to present a discussion of the various approaches that can be taken in the study of mine subsidence phenomena. Particular attention is focused upon the rational selection and use of laboratory models. Broadly interpreted, mine subsidence is the deformation of the rock mass enclosing a mine. Depending upon a number of factors, the movement of the subsiding rock mass may disrupt gas and water lines or other buried utilities, damage surface structures such as buildings and bridges, dislocate streams, roads, and rail lines, aggravate acid mine drainage and fire problems, and generally mar the landscape. It is clearly a problem that no mine manager can safely ignore. It is also a problem that will grow with the general population increase. In the following discussion, a summary review of past and present approaches to subsidence studies is given. The possibilities of duplicating subsidence phenomena in laboratory models are examined, and an analysis of a particular type of model is presented. Some preliminary results obtained from a model of the particular type analyzed are then discussed. REVIEW OF PREVIOUS WORK Historically, subsidence investigations have been empirical studies in the field and laboratory or theoretical analyses of mathematically idealized media. Empirical and theoretical work in the United States has generally lagged behind investigations abroad. In the United States, field studies are mostly pre-World War 11. These are summarized in the Mining Engineer&apos;s Handbook. &apos; Field studies in Europe are more recent and more extensive. Those made in Great Britain are summarized in the Subsidence Engineers Handbook2 and represent observations made at 157 different collieries. Such studies by themselves are of limited usefulness as are all empirical studies. One can never be certain that conditions at one mine will be similar enough to those at another to warrant the drawing of like conclusions. European subsidence formulas rely heavily upon the "angle of draw" and "critical area" concepts. The angle of draw is defined as the angle between a vertical line through the face, and another line extending from the face to the surface at the point where movement is zero. The critical area is defined in relation to the least extraction necessary to produce maximum subsidence. Fig. 1 illustrates the angle of draw and critical area concepts. First and second "limits of influence" are also shown. The angle of draw and associated critical area concept are obviously not well defined, being dependent upon the accuracy of the surface survey. In Great Britain, the angle of draw has increased through the years from about 26 to 35°. In the United States, zero and negative angles of draw have been reported. In the authors&apos; opinion, these purely geometrical concepts represent an oversimplification of subsidence phenomena and their use, in the United States at least, should be discouraged. Empirical observations of laboratory models containing layers of earth, sand, clay, and plaster were made by Fayol (cited by Peele) as early as 1885. An outgrowth of his work was the "dome theory," a verbal description of what is assumed to occur in subsiding rock masses. The dome theory has since fallen into disrepute. Theoretical analyses worthy of the name treat a subsiding rock mass as a deformable body. In these analyses, the actual rock mass is replaced by an idealized material that deforms according to a simple stress-strain relationship. The stress equations of equilibrium expressing the Newtonian laws of mechanical action and the geometry of strain furnish additional equations that must be satisfied. A loading criterion-generally understood, and in some cases stated explicitly-completes the theory.

Jan 1, 1969

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer&apos;s method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By P. B. Baxendell

The performance of a water-drive reservoir having a gas cap depends primarily on the movement of the gar-oil and oil-water contacts. The movement of the contacts during production depends in turn on fluid withdrawals and how the reservoir pressure changes as fluids are produced from the reservoir; that is, on how effectively the aquifer maintains pressure by replacing withdrawals. inasmuch as pressure changes, fluid withdrawals, contact positions, and produced gas-oil and oil-water ratios are interdependent, the analysis and prediction of the performance of a reservoir produced in a given way must take into account this interdependence throughout depletion. This paper presents an analysis which, within the limitations of the assumptions made, yields an engineering approach to predicting future performance based on reservoir pressure and production history. The most significant assumption is the method of extrapolation of future gas-oil and water-oil ratios. The extrapolation procedure smoothly increases both ratios to preselected values as the remaining oil column undergoes a specified decrease in thickness. This preselection is made on the busis of previous field experience in depletion of similar reservoirs under similar conditions. For computing future performance a vdumebic balance L combined with the differential equation defining pressure distribution in the aquifer to obtain positions of water-oil and gas-oil contacts. From these positions are extrapolated produced water-oil and gas-oil ratios. Reservoir performance can be investigated when oil production rates are dependent upon various factors including the performance of the reservoir itself. Examples of practical application of the procedure are included. INTRODUCTION To predict performance of water-drive reservoirs with gas caps and thin oil columns, it is necessary to describe the motions of the fluids within the reservoir during the entire production period to depletion. These motions depend on the pressure changes and on the withdrawal of oil, gas and water. Production of oil from the oil zone primarily causes water to move in to take its place; production of gas from the cap tends to cause oil to migrate into its place. In addition, the volumes of oil and gas remaining in the reservoir depend on changes in the pressure, since a decrease in pressure causes fluid expansion, gas liberation and oil shrinkage. A method of relating the future pressure to total withdrawals is used to describe the motions of fluids within the reservoir under conditions arising in possible modes of production. The analysis is based on two relationships and will reduce the problem to one amenable to digital computation. The first of these concerns the dependence of the pressure distribution in the entire aquifer furnishing the water drive upon the total reservoir withdrawals. This dependence is dictated by the permeability distribution and the extent of the aquifer; at present, such information is most readily obtained from the performance history by means of the resistancecapacitance reservoir analyzer. The second relation involves withdrawals, pressure in the reservoir, and movement of oil, gas, and water within the reservoir. The analysis is subject to certain simplifying assumptions that are necessary to permit solution of the problem. A comparison of the methods of this paper with those presently practiced is pertinent. One method of analysis is to use the reservoir analyzer to predict reservoir behavior based on aquifer characteristics determined from production history. Inasmuch as the total withdrawal rate depends upon the gas-oil and water-oil ratios, which depend in turn upon, among other things, the positions of the gas-oil and water-oil contacts, these ratios must be assumed in advance. In this paper these ratios are, instead, related to the computed positions of gas-oil and water-oil contacts. Thus, our method can be applied to problems in which the oil production rate is limited by produced gas-oil ratio, or to problems in which it is desired to determine the variable gas injection rate that will maintain the gas-oil or water-oil contact stationary. These problems cannot be worked satisfactorily on the analyzer. Another method presently used is based on a paper by Hurst.&apos; Since his procedure is dependent upon using the solution of the heat flow equation, which requires constant permeability within the aquifer, and our procedure recognizes variations of permeability in

By David A. Thomas, John F. Peck

Fibrous microstructures and their development have been studied by metallography and by hardness and quantitative metallographic measurements. Thin, curved grains were observed in transverse sections of commercial tungsten wire and were developed in laboratory-drawn iron wire at reductions greater than about 70 pct. The unusual grain shapes are attributed to the nonuniform mode of deformation of the grains associated with the characteristic [I101 preferred orientation that develops in bcc metals during drawing. Transverse sections of heavily swaged iron wire showed a ospiral nebulao structure that appears to result from the elliptical shape of the cross section of the swaging dies and their rotary motion. Hardness and quantitative metallographic results show unusual trends that parallel the changes in microstructure. Other phenomena are considwed in light of the results, including the strength of fine wires of bcc metals, ocylindricalo textures, and the ductility of fibrous tungsten. 1 HE microstructure of tungsten wire in a longitudinal section shows grains highly elongated in the working direction, giving the appearance of a bundle of parallel fibers, Fig. l(a). Wires of tungsten and other bcc metals show a pronounced preferred orientation in which a [I101 direction is parallel to the wire axis.l The microstructure and texture of tungsten develop during warm working (working above room temperature but below the recrystallization temperature) into wire by swaging and drawing. Fibrous tungsten so produced has limited but useful room-temperature ductility, whereas annealed tungsten is brittle at room temperature. During an investigation of the effect of recovery annealing on the substructure of commerical 0.030 in. diam tungsten wire, it was found that transverse sections of the as-received material showed thin, curved grains, Fig. 1(b), instead of the expected equiaxed grains. The fact that Figs. l(a) and (b) show different sections of the same material at the same magnification is at first disconcerting, because the long dimension of the curved grains in the transverse section is several times the average fiber width in the longitudinal section. However, a longitudinal section cuts most of the curved grains across their narrow dimension, giving the appearance of a multitude of narrow fibers. On the other hand, the plane of a longitudinal section occasionally includes a long dimension of a curved grain, resulting in a broad ofibero, such as A in Fig. l(a). EXPERIMENTS AND RESULTS To investigate the origin of fibrous microstructures and particularly the unusual transverse-section structure of tungsten, rods of iron (also bcc) were drawn and swaged in the laboratory. One rod of annealed Ferrovac E was drawn in six steps to a total reduction in area of 87 pct (0.10 to 0.036 in. diam), and a second rod was swaged to the same reduction, using approximately the same reduction steps. Longitudinal and transverse sections of the swaged and drawn iron wires are shown in Fig. 2, for reductions in area of 39, 73, and 87 pct. A fibrous microstructure in longitudinal section is first evident at 73 pct reduction, and it is further developed at 87 pct reduction. The grains in transverse section remain equiaxed until about 73 pct reduction, when they become somewhat elongated and curved. At 87 pct reduction, the drawn wire shows thin, curved grains in the transverse section, similar to those observed in tungsten. The transverse sections of the iron wires swaged 83 and 87 pct reduction in area show the striking ospiral nebulao structure in Fig. 2(d). This struc-

Jan 1, 1962