Search Documents

By J. W. Halley, G. L. Plimpton

BECAUSE of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. MECHANISMS PRODUCING SEGREGATION The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1944

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel'd and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

By John Chipman

IN the manufacture of rimming steel-which constitutes the bulk of the world's production of mild steel-the factors that determine the quality of the product are very closely associated with the pouring and solidification of the steel in the ingot mold. The behavior of the metal in the mold is, on the one hand, the resultant of the complex processes through which the liquid metal has passed, and, on the other, it is an indication of the probable behavior of the ingot during subsequent rolling and finishing operations. A detailed study of the mechanism of solidifica-tion of rimming ingots ought to yield information that will be useful iii controlling the structure of the ingot and the quality of the ultimate product. The first step in such a study is to determine the rate at which the solid shell of the ingot forms from the liquid metal in the mold. A knowledge of the rate of solidification will make it possible to correlate observations of rimming action and gas evolution with studies of the structure, porosity, and segregation within the ingot. Thus, if the metal in the mold is observed to fall, let us say one minute after pouring, the portion of the structure associated with this fall will lie located in the part of the ingot that is solidifying at that particular moment. The knowledge that the ingot solidifies to a depth of ¾ in. in the first minute enables us to locate in the ingot the structural features corresponding to the observed fall. Conversely, the blowhole condition associated with a rising or growing ingot will be found in the part of the ingot that is solidifying at the time the phenomenon occurs. The time required for the complete solidification of an ingot has long been a matter of speculation. It is of considerable practical importance in connection with charging and heating in the soaking pits. Too rapid handling of the ingot through heating and rolling processes has been thought to be associated-with excessive pipe and other internal defects, so that a further object of this investigation was to attempt to estimate the time required for complete solidification, or the minimum practical time within which the subsequent operations can be performed with the minimum hazard.

Jan 1, 1937

By James R. Jones

The concern for air pollution goes back centuries as will be seen from this quotation : "Strife and coal, it seems, have a hand-in-hand historical relationship. It was thought by some . . . in the Middle Ages that burning coal filled the air with dangerous poisons. So great was the concern that in 1306 King Edward I of England passed the first and unquestionably the harshest air pollution legislation edict that history will record. His proclamation declared the use of coal an act punishable by death." As related to coal mining, the air pollution problem is primarily that of its customer when using the fuel. Thus the major impact relates to markets for coal rather than the actual mining operation itself. In the vicinity of the coal mine the problem is principally related to fugitive dust from roads, transfer facilities, loading facilities, crushers, etc., and particulate matter (dust or fly ash) from thermal dryers and air cleaning tables. FUGITIVE DUST Most state air pollution regulatory agencies now have rules and regulations requiring control of fugitive dust. Fugitive dust has been defined by the courts as particulate matter other than that emanating from a specific point such as a stack or chimney. A typical air pollution control agency regulation reads as follows : “Fugitive Dust " "No person shall cause, suffer, allow, or permit any material to be handled, transported, or stored; or a building, its appurtenances, or a road to be used, constructed, altered, repaired or demolished without taking reasonable precautions to prevent particulate matter from be- coming airborne. Such reasonable precautions shall include, where applicable, but not be limited to the following:

Jan 1, 1981

By Wiley C. Buford

Gary Works No. 1 BOP Shop is a three furnace shop which went into operation December, 1965. The heat size is over 200 tons, with a substantial percentage of the production used to feed a Continuous Slab Caster. Vessels are driven by a shaft mounted bull gear and main housing utilizing eight 35 HP flange mounted motors and primary gear reducers. Torque absorption is controlled by two spring actuated torque arms. At 1:00 p.m. on Thursday, August 6, 1970, as "E" furnace was being turned down for a preliminary test, the drive side trunnion bearing failed. The furnace dropped slightly and shifted several inches north in the direction of the drive unit. The decision was made to tap the heat which was done without incident and the vessel uprighted. No attempt was made to completely drain the slag from the vessel, so as to avoid any further damage to the trunnion shaft bearing surface. The bearing failure occurred approximately four years and eight months after start up of the shop. Unfortunately ?M? furnace had gone down for a normal reline two days prior to the bearing failure, leaving the shop with only one operating furnace.

Jan 1, 1972

By A. K. Mukherjee, J. E. Dorn

A modified Peierls model is Presented for the rationalization of the asymmetric plastic behavior of single crystals of bcc metals. The model assumes that the asymmetry of slip arises from a tendency toward asymnetric splitting of the a/2[111] screw dislocation. The approach differs from former theories however insofar as it assumes that the splitting is so minor ttut only the core energy is modified and that no real partial dislocations exist. As a consequence, the concepts of a line energy of a partial dislocation, interaction between partial dislocations, constriction energies, and stacking fault energies are not invoked. Instead the present analysis is based on a specialization of the Peierls mechanism which assumes an asymmetric dislocation core which is modified by the effective stress and permits cross slip. The theoretical predictions on the stress-temperature -strain rate and orientation relationship agree qualitatively with the limited experimental data that are currently available. Additional experimental work over wider ranges of conditions is suggested to provide more complete evaluation of the possible validity of this theory. RECENT experimental investigations on the low-temperature thermally activated deformation of bcc metals have confirmed the existence of several unique orientation effects. These will be described with the aid of the standard stereographic projection shown in Fig. 1. If slip were determined exclusively by crystal symmetry, the deformation characteristics would be symmetrical about X; = 0 and independent of whether the specimen were subjected to a tension or a compression stress, regardless of what combinations of slip planes might be operative. Experiments, however, reveal that neither of these symmetry based predictions are valid. A schematic representation of the commonly observed asymmetry of both the yield stress and the plane of slip is shown in Fig. 2. A reversal of the direction of stressing results in an inversion of the asvmmetric behavior. 1) Asymmetry bf Yielding. A detailed investigation on the asymmetric yielding in an Fe-2.7 pct Si alloy was repoEted by Tabka, Tikeuchi, and Furubayashi,1 Similar trends have been observed by Keh and Nakada on iron,' Stein on molybdenum,3 Bowen, Christian, and Taylor4 on columbium, Sherwood, Guiu, Kim, and pratt5 on Ta, Cb, and Mo. The degree of asymmetry not only depends on the atomic number and alloying but, in all cases that have been examined, it also increases with a decrease in the test temperature. 2) Asymmetry of the Slip Plane. Asymmetric $I-~: curves of the type shown in Fig. 2 have been found for several Fe-Si alloys6-8,1 and columbium.4 There is general agre_ement that near X: = 30 deg slip occurs by the [111](211) mode so that ?1 = 30 deg. As X; decreases it appears that [111](211) to [111](101) cross slip takes place leading to slip band traces on intermediate planes. And as xi approaches 0 deg, sharp

Jan 1, 1970

References are in all cases to the earliest known editions. In the few cases where the first edition has been unavailable for consultation, the particular one studied is indicated. English translations are included when known, but not others. [ ]

Jan 1, 1942

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

By Charles Eichrodt

THE ore that is being treated by the present plant lies between the leached zone, or capping, and the mixed sulfide and oxide zone. The principal copper minerals are chalcanthite (CuSO4.5H20), brochantite (CuS04 3Cu (OH)2) and atacarnite, (CuC12.3Cu (OH)2). There are, in addition, some other minerals such as cuprite and kröhnkite (CuSO4. Na2SO4.2H20). These minerals, with many others, occur in a greatly crushed granodiorite rock. Most of the copper-bearing minerals occur in the cracks and veinlets, but there are disseminated values and it is probably the relative proportion of these that accounts for some otherwise unexplainable variations in extraction. The entire mineralization of the ore is complex and varies with depth. This variation, the problems presented thereby, and the effect of various constituents of the ore will be taken up in detail. An analysis of an unweighted composite of the ore treated during 1927 follows:

Jan 1, 1930

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By R. Wiesenthal

A method is developed for improving the low recovery efficiency which results when viscous oils are flooded by water. Viscous oil has been diluted with a lighter liquid miscible in it in any ratio which produces a mixture possessing a reduced viscosity and which is then displaced by water. Light gasoline was used in these tests to reduce the viscosity of the oil in place. Oils possessing viscosities in the range of 1.28 to 324 cp at the test temperature of 30C were displaced from a cylindrical unconsolidated sand core, with a length of 2 m (6.6 ft) and a diameter of 10 cm (3.9 in.) at a flood of 6.27 cc/sq cm/hr. In two test series up to I PV of light gasoline was injected into the core before water flooding. In the first series the recovery of a low-viscosity oil (1.28 cp) increased as the volume of light gasoline was increased. However, only the oil which could not be recovered by water flooding alone could be replaced by the light gasoline. In the other series, the recovery of a more viscous oil (13.5 cp) was not increased even if large quantities of light gasoline were injected. An oil bank built up ahead of the water front so that the flood water met with equivalent saturation conditions, as would be the case in flooding solely with water. However, the recovery of more viscous oils could be increased substantially when the core was first flooded with water, followed by a slug of light gasoline, and then flooded with water again. Furthermore, an oil bank ,built up ahead of the second water front. The formation of this oil bank is particularly favorable for the displacement process; the greater part of the light gasoline injected was pushed out of the core ahead of the oil and recovered. Using a light oil of low viscosity, it was possible to replace only the residual oil that could not be recovered by water flooding by the light gasoline. As the basic study had shown that highly viscous oils could be recovered by flooding first with water, then with light gasoline, followed by a second injection of water, the study was extended by tests made with reservoir fluids and cores taken from the low-gravity oil reservoir of the Wietze field, Germany. A great increase in recovery over flooding with water alone was obtained in these tests. The results may show a way to recover high-viscosity oils by a comparatively simple flooding procedure. INTRODUCTION In fields where oil recovery has not benefited from natural water drive, increased recovery may be obtained by the injection of water into the reservoir, especially in the case of fields which produce high-gravity, low-viscosity oil. There is a rather close relation between the viscosity of the reservoir fluid and the recovery that can be obtained by water flooding. As the viscosity increases the oil recovery decreases proportionately, so that an oil viscosity about 30 times that of water is generally considered to be the upper limit for an economically successful water flood.' This limitation has been recognized theoretically by Buckley and Leverett,' and has been verified by numerous laboratory flooding tests, such as by Croes and Schwarz,V n the viscosity ratio range of oil to water from 1 to 500. The reason for the inferior recovery of viscous oils by water flooding can best be understood by considering the mechanism of flood tests. In such tests water is introduced into one end of a sand-packed tube which is saturated with oil of the viscosity to be tested, and oil is produced from, the other end. Oil, with a viscosity lower than that of water, is pushed ahead of the advancing water with considerable uniformity, and irregularities in the displacement process tend to be eliminated as the oil saturation decreases and the water saturation increases. However, oil recovery is not complete, for the water forms interfaces with the oil and traps residual oil droplets in certain of the pore spaces. These residual oil droplets are distributed rather uniformly through the sand, and they are not susceptible to recovery regardless of the amount of water passed through the test cylinder. In the case of an oil possessing a viscosity greater than that of water, the injected water tends to move irregularly through the sand in the test cylinder. At the place in the sand where initial water movement takes place, resistance to the movement of water is lowered and the water finger so formed will grow perceptibly; it will extend to the outlet end of the test cylinder so that a breakthrough of water takes place long before much of the oil-saturated volume of the sand has come in contact with water. Once the breakthrough of water takes place, the water-oil ratio is gradually approaching the economic limit, even though much of the oil in the test cylinder remains unaffected by water. Disconnected drops of oil are trapped in the portion of the sand that has been invaded by water, just as when an oil of low viscosity is flooded. The poor recovery of the more viscous oils, therefore, is due to the irregularity of water movement through the test cylinder, and the rate of water movement through restricted sections of the oil-saturated sand increases with the more viscous oils. There are three ways whereby the recovery of viscous oils by water flooding can be improved:' (1) adding materials which will increase the vis-

Jan 1, 1965

By Herbert R. Hanley

THE One Hundred and Twenty-sixth meeting-of the Institute, held in San Francisco, Sept. 25 to 29, 1922, was a success in every way. Character-istically, San Francisco presented climate suited, to the occasion, while the Committees on Arrangements left nothing undone that would contribute to the interest and entertainment of the members and their wives. There was a registration of over 230, and all sections, save three, were represented. In the technical meetings, under the leadership of Albert Burch in the mining session and C. W. Merrill in the milling session, the greatest interest was manifested in ore-hunting geology and modern ore-dressing methods. The general geologic phase developed numerous discussions and had for its aim the study and correlation of known data and the application-of these to the finding of commercial orebodies. The geologic features of the Comstock and their significance to the development of the present orebodies were discussed. This brought out matters of much technical interest as well as those of romantic nature in the history of the early life of that camp. The profitable application of modern milling methods to ores, non-commercial a short time ago, was discussed with much interest. The recent work on the Comstock ores occupied a conspicuous part in these discussions. Basic principles delineated by mathematical study of mechanical devices for the milling of ore came in for a prominent part in the program as well as the physical-chemical side of the processes devised for the winning of precious metals as a profit.

Jan 11, 1922

By Frederick L. Knouse

THE south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19° to 21° and 30" south latitude; and from 40° to 41° and 30" west longitude. This includes the central part of Espirito Santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Martines, Espirito Santo (Fig. 1). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through Vitoria; and by the E. F. Minas-Vitoria and E. F. Central do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatites, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. EARLY OPERATIONS Mining of quartz crystal in this region began in 1928, and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crystal as small as 10 grams. Since 1941 only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of loo grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, or Domingos Martines, Espirito Santo. Marketable quartz crystal was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large cores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. PRODUCTION The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1946

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By S. J. Green, R. D. Perkins

Little data exists on the high strain rate behavior of geologic materials. Uniaxial stress tests by Kumar1 and by Serdengecti and Boozer2 present some results to strain rates in the range 10 to 103 per sec. The two references cited are the only ones the authors found for high strain rates. Techniques for experiments at high strain rates are not well developed and, in general, leave questions with respect to interpretation of data when the material behaves in a brittle manner. The most reliable data at very high strain rates (104 to 106 per sec) are found in some recent flat-plate work3-5 where experimenters have impacted one plate into another, thereby creating a uniaxial strain loading. The standard uniaxial stress-strain curves cannot be obtained directly from these tests; however, yield (or fracture) may be studied by measuring the "elastic" wave magnitude. These data then may be compared to uniaxial stress data by resorting to some preassumed yield/fracture criteria. Even with the most liberal interpretation of existing data, little can be said of the effects of high strain rate on stiffness, yield/fracture, and post-fracture behavior of geologic materials. It is the purpose of this work to begin to add to the understanding. The data presented here are intended to provide material information for use in calculating the response of geologic materials to high rate deformations. These data can be applied directly to determine parameters such as the elastic modulus and Poisson ratio as a function of stress. Furthermore, these data can be used to derive an understanding of yield/fracture and the effect of rate on the yield/fracture surface. The work presented is a first step, and is

Jan 1, 1972

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970