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By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2 by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn = MnO + Fe [A]slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aMoO aFeI1 dFec) aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term [afe] may be combined with K" to give a new constant K'. Making these changes,

Jan 1, 1942

By L. C. Kern

This paper presents information on the use of a new propping agent (malleable aluminum particles) which has been used successfully for producing high-conductivity fractures. The conductivity of a packed fracture depends on the width of the fracture as well as the permeability of the propping material. It is significant that the flow capacity of a propped crack is often increased many fold by propping the crack with a sparse distribution of particles. However, the flow capacity of a sparsely propped crack can be limited by two phenomena: (I) crushing of the propping particles, and (2) embedment of the propping particles in the formation walls. Malleable aluminum particles exhibit interesting properties which tend to overcome these limitations. As high loads are applied to the particles they will deform slightly, rather than shattering. The deformation results in a greater bearing area against the formation wall. This reduces the stress on the particle and reduces particle penetration into the formation. The behavior of aluminum particles under load and the bearing capacities of serveral formation rocks have been measured in the laboratory. By properly using these data, as explained in this paper, the flow capacities of aluminum-propped cracks can be calculated for a variety of conditions. Aluminum particles have been used successfully in the field to prop fractures. Where high-conductivity fractures were needed, the aluminum-propped fractures have given greater well stimulation than could have been expected for conventional fracturing processes. INTRODUCTION The purpose of a hydraulic fracture treatment is to create a conductive channel from the wellbore out into the oil or gas formation. The word conductive is emphasized because we believe that the fracture conductivity (flow capacity) is one of the most important factors influencing fracturing results. Previous papers have pointed out the additional well stimulation that can sometimes be achieved by increasing fracture conductivity. Several years ago, we investigated in some detail the effect of fracture conductivity on productivity increases to be expeced from vertical fractures. Both electrical analog and theoretical studies of unsteady-state flow behavior were made. A discussion of the electrical analog equipment and some of the results of the study were given in a previous paper' by Dyes, Kemp and Caudle. Further details were given recently by McGuire and Sikora.5 Fig. 1 shows the remarkable influence of relative fracture flow capacity and length on well stimulation. Briefly, the study indicates the following. 1. High-permeability formations require high-conductivity cracks for best results. 2. The longer the crack, the higher the fracture conductivity required for best results. 3. If the conductivity of the crack is very large compared to the formation (i.e., flow is not being limited by crack conductivity), then the longer the fracture, the better will be the results. Judging from recently published articles,1,314 there is current interest in methods for obtaining high fracture conductivities. Hence, we would like to present in this paper a discussion of a new fracture propping process (use of aluminum particle) which we have used successfully to obtain highly conductive fractures. There are several factors which influence the conductivity of a propped crack. Conventional fracturing techniques frequently result in a crack completely packed with fracturing sand. For such conditions, the crack conductivity is the product of the width of the packed fracture and the permeability of the propping material. It is significant that a large increase in conductivity sometimes can be obtained by propping with particles which are distributed sparsely (less than a

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By M. W. Bartley, Hugh M. Roberts

SUBSTANTIAL deposits of Bessemer hematite have been found recently by drilling beneath Steep Rock Lake, Ontario, which is situated in the northern part of the Lake Superior Region. It will be practicable to divert the waters flowing into this lake and develop open pits on the upper part of two large ore bodies by damming off and pumping out the water in the part of the lake in which they occur. Ultimately, the bulk of the ore will be mined by underground methods. Owing to the generally massive nature of the rocks in the area, no underground flows of major consequence are anticipated after diversion of the lake. The Steep Rock deposits are attributed in origin to hydrothermal replacement. They were formed, for the most part, along an unconformable, brecciated contact between the Steep Rock limestone and an overlying younger volcanic series. The replacing solutions came in as igneous after-effects, following upon the intrusion of basic igneous rocks that invaded the hanging-wall volcanics. It is believed that this took place in a geological period roughly equivalent to late Middle Huronian, which was the period when the most extensive iron-bearing rocks of the Lake Superior Region were formed. Comparison is made with other deep-seated iron-ore bodies in the Lake Superior Region, the origins of which are ascribed in the discussion to hydrothermal replacement.

Jan 1, 1943

By B. W. Gandrud

WET-PROCESS coal-washing tables as we know them today have been in use in this country for approximately 25 years. The literature records only a few table installations worthy of note prior to adoption of the present-day differential-motion table. According to Phillips,' six Campbell bumping tables were being operated by the St. Bernard Coal Co., Earlington, Ky., in 1893. As late as 1923, according to Richardson, 72 such tables were in operation in the Rosedale washery of the Cambria Steel Co., at Johnstown, Pa. Bumping tables probably were not used to any considerable extent except in the plant at Earlington, and at two or three plants in Pennsylvania, but they may be considered as forerunners of the present-day coal-washing table. The transition from bumping tables to the type of tables now in use signalized a revolutionary change iii table design. The advantages of the new design over the old were so outstanding as to make its adoption inevitable. BUMPING TABLES Bumping tables, as the name implies, utilized a bumping action for conveying the refuse and discharging it over the refuse end. The tables were hung from rods attached to overhead supporting beams. A shaft and cam arrangement at one end of the table served as ,the actuating mechanism and imparted to the table an endwise, back-and-forth, swinging motion. A bumping block was fixed in the proper position at the shaft end, so that the table would strike against it at the end of each backward swing. The hanger rods or stirrups were so adjusted as to give the table a slight uphill slope toward the refuse end; that is, the end next to the driving mechanism. The feed box was near the upper end of the table and designed to spread the mixture of coal and water over the width of the table. Wash water was added a short distance below the feed box. With the table in motion and coal mixed with water being fed to it through the feed box, a certain amount of stratification took place, depositing heavy refuse at the bottom of the bed in contact with the surface of the table. Constant bumping and a certain amount of

Jan 1, 1943

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 Van Dyne Howbert, Fred E. Gray

The Presidio mine of The American Metal Co. of Texas is situated 45 miles south of Marfa, Texas, a town on the Southern Pacific R. R., and lies approximately 20 miles north of the Mexican border. Communication with the railroad is maintained over a state highway. All supplies for mine and mill are hauled in by truck from Marfa and precipitates and concentrates are freighted to the railroad by the same means and shipped to Selby and El Paso, respectively. The mill is at the town of Shafter, 1 mile from the mine and at approximately 350 ft. lower elevation. The ore is conveyed to it by an aerial tramway which requires practically no power on account of the difference in elevation. The mill is a countercurrent decantation cyanide and gravity concentrating plant of 200 tons daily capacity. Coarse and fine crushing are done at the mill. Two neal-by shallow wells in the bed of Cibolo Creek furnish an abundance of water. Power is generated for the mill and town by a Diesel engine plant. Ore Treated The ore is oxidized and siliceous. The greater part contains approximately 16 oz. of silver per ton, but mixed with this are many particles of ore of much higher grade, assaying in many instances 100 oz. or more. In the 16-oz. material there is an almost constant amount of silver which is difficult to recover by cyanidation. The high-grade material contains a much greater proportion of silver which is easily amenable to cyanide treatment. Thus, as the grade of ore becomes higher, the percentage of recovery of silver increases rapidly, under equal milling conditions. The silver minerals contained in the ore are principally argentite and cerargyrite, the former predominating The lead minerals, all of which are argentiferous, are chiefly cerussite and galena, with occasionally a little anglesite. The gold is free; most of the ore contains merely a trace

Jan 1, 1935

Mining headlines in 1952 dealt mainly with expansion as the industry aimed for an ever increasing production to meet the nation's needs. Huge sums were expended for equipment, research, and development. Headlines told part of the story. Negotiations between San Manuel Copper Co. and the RFC finally resolved in a $94 million loan for the development of low grade Arizona ores. Magma Copper, parent firm was to supply an additional 8 million. Kennecott Copper Co., deepening its Deep Ruth Shaft of its Ruth, Neyy mine, announced that the shaft would be in full production in 1953.

Jan 2, 1953

By William Phillips

THE earliest mention of the sulphur deposits in what is now Culberson County, Texas, seems to be contained in "Explorations and Surveys for a Railroad Route from the Mississippi River to the Pacific Ocean, United States War Department, 1853-54." Captain John Pope (he was not commissioned Captain until 1856) had charge of one of the divisions of the Survey. In his report on the geology of the route, William P. Blake noted the analysis of a greenish earthy powder from the bed of Delaware Creek, at the springs, which contained 18.28 per cent. of free sulphur. The report states: "From the chemical examination of the waters of the spring, by Dr. Booth, it appears that chloride of sodium is the principal solid ingredient, but considerable quantities of sulphide of sodium are present. * * * * * The waters from the springs examined by Dr. Booth were alkaline, but it is possible that some of the springs are acid; and in this case the precipitation of sulphur would ensue on the mixture of the acid waters with those charged with alkaline sulphurets and the origin of the deposits of sulphur would he thus explained." This is the first reference to the existence of sulphur in that region, the first mention of the character of the water found there and the first suggestion as to the' origin of the deposits. The possibility of the existence of acid waters was confirmed by E. M. Skeats, nearly 50 years later.1 In this publication, Skeats says that the water from the sulphur deposits in Section 11, Block 114,, Township 5, contains 79.08 grains of free sulphuric acid per gallon. This locality is about 13 miles (21 km.) south of Delaware Creek and about 35-miles (56 km.) east of the Delaware Springs. The next published reference to the existence of sulphur in Trans-Pecos Texas is in the First. Annual Report of the Geological Survey of Texas, 1889, page 226, where W. H. von Streeruwitz mentions that sulphur is found in that region, but gives no further information. In the

Jan 9, 1917

By G. E. Anderson

The Asientos-Tepezala district is in the north of the State of Aguasca-lientes, about 30 miles north of the city of Aguascalientes, the capital. The district is reached by a standard-gage railway on the west side through the junction, Rincon de Romos, which is on the main line of the National Railways of Mexico from El Paso to Aguscalientes. The terminal is Tepezala. On the east side a narrow gage connects Asientos with the junction, San Gil, on the main line, Asientos to San Luis Potosi. Tepezala on the west side of the Asientos hills is about 2 miles from Asientos on the east side. The area between the two mining centers is separated by a low subdued divide which forms the central part of the hills. The district is in a group of isolated hills surrounded by characteristic bolsón plains. The hills rise above the surrounding plains about 6500 to 10,000 ft.; the highest peak is Alta Mira. The two mining districts lie somewhat upon the flanks of the hills at about the same elevation, 7200 ft. The district is an old one and has been known since early in the 17th Century when the mines were worked by the Franciscan Monks. Their mining operations, which were limited to the oxidized ore above the water level, consisted chiefly in extracting silver from the Santa Francisca vein. To judge from the old workings and the remains of surface plant, the operations were on a large scale. By modern mining operations since about 1900, the various mines of the district have been one of the principal sourees of ore for the smelter located at Aguascalientes. Topography The topographic features of the Asientos hills are largely controlled by the character of the underlying rocks. During the Tertiary period, the entire group of hills was probably covered by extrusive volcanic material in the form of cones and lava flows. The central part of these have since been carried away by erosion, so that remnants have been left along the borders of the hills. These remnants form rather conspicuous peaks,

Jan 1, 1927

By Owen F. Devereux

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

Jan 1, 1969

By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs' scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

By R. M. Sellwood

The No. 4 I.S.F. Smelter Complex at the Avonmouth Works of Imperial Smelting Corporation (N.S.C.) Limited commenced operation at the beginning of 1968. The furnace rating is 120,000 tons zinc and 40,000 tons lead per annum. Zinc and lead concentrates are unloaded onto a 1,000 tons per hour capacity conveyor belt and automatically weighed and sampled before receipt into a 48,000 ton capacity raw material store. Distribution is by a reversible boom stacker into 16 x 3,000 ton bays and recovery is by a front end loader. Materials are fed to 16 proportioning bins for feeding via continuous weigh feeders to a 132 square metre effective updraught area sinter machine with a material flow rate of 240 tons per hour over the machine. The required quantity of output lump sinter at up to 800ºC is fed to 2 x 600 ton storage bins on the I.S.F. plant. By-product SO2 rich gas is fed to a conventional wet gas single stream acid plant rated at 600 tons per day utilizing a dry N.T.P. gas volume of 100,000 cubic metres per hour. The hot sinter and preheated coke (800ºC) are automatically neighed and charged to a 27.3m2 shaft area I.S.F. fitted with 2 x 5.5 m. wide lead splash condensers. Grade 4 zinc is tapped and transferred to the zinc refinery. Conventional type lead bullion and slag are tapped from the bottom of the furnace through a separation forehearth. The refinery consists of 6 lead and 3 cadmium columns to produce some 52,000 tons per annum of S.H.G. metal. S.H.G. metal and Grade 4 metal is cast into various shapes as required.

Jan 1, 1970

By W. T. Allan

RAW bituminous coal has been in general use as a blast-furnace fuel in Scotland for the last century, and although its use has now been largely abandoned and it has been replaced by coke in the majority of the few furnaces which are at, present in blast in this country, coal-smelted pig iron is not yet a thing of the past; it is still being produced and mar-keted in competition with the more cheaply smelted product of the coke-fired furnace. Various factors have influenced this change in practice; the once plentiful deposits of coal of a suitable nature for the blast furnace are now not so easily obtainable; native blackband and clayband ironstones which are easily smelted in the coal-fired blast furnace, although still far from being exhausted, are not available except at a. cost that is somewhat higher than that of imported ores, making them unattractive to the ironmaster that is compelled by circumstances to smelt his iron at the lowest possible cost. Within the last 15 years overproduction of synthetic nitrogen has led to progressive reductions in the price of sulphate of ammonia, the recovery of which together with the other by-products before that time materially assisted in reducing the working costs of the coal-fired furnace. Now the sale of the by-products recovered yields a diminished profit. When the cost of the product is the only consideration the small, slow-smelting, coal-fired blast furnace cannot compare with its large, modern, coke-fired competitor. Other `considerations do not by any means all support the same side of the argument. In the smelting of pig iron to be used in the manufacture of steel where the quality of the final product depends so largely upon the control of the conversion process and so much less upon the physical quality of the pig iron used, the physical properties of the pig iron do not exert any appreciable influence upon the quality of the steel produced, therefore the methods employed in the smelting of the pig iron matter but little so long as the requisite chemical composi-tion is reached. On the other hand, in ironfounding where the simple melting of the pig iron, which is the only treatment it receives before being cast into its final form, does little or nothing to modify its original charac-

Jan 1, 1937

By E. M. Wise

MANY of the platinum metal alloys are hot-forged in the early stages of reduction from ingot and substantial quantities of platinum alloys are commercially employed at very high temperatures in ammonia oxidation units, orifices for forming glass rods and fibers and as cathodes in long-life thermionic amplifiers. They are used also for electrical heating resistors, safety blowout disks, thermocouples and crucibles. The tensile prop-erties at elevated temperatures are important in many of these situations but data on the subject are limited. Creep data also are important, but will not be covered at this time. SCOPE AND CONCLUSIONS Tensile tests were carried out at room temperature and elevated temperatures up to 1100° C. on previously well annealed samples of platinum, palladium and several of their important alloys with composi-tions shown in Table 1. The results are presented graphically in Figs. 1 to 4. The tensile strengths of platinum and the platinum-base alloys (with the exception of the 10 per cent rhodium-platinum alloy) at 1100° C. are from 16.6 to 18.8 per cent of the strengths of the same alloys (well annealed) at room temperature. The strength ratio of the 10 per cent rhodium-platinum alloy is 22.3 per cent, which is appreciably higher than that of the other materials tested.

Jan 1, 1938

By W. G. Pfann

Under certain conditions, a molten zone can be made to move through a solid by impressing a stationary temperature gradient across the solid. This phenomenon can be utilized in fabricating semiconductive devices, growing single crystals, joining, boring fine holes in solids, measuring diffusivities in liquids, small scale alloying, and purification. Fundamentals and exemplary applications are outlined. ANEW aspect of the travel of a molten zone through a solid is considered in this paper. Whereas, in previously described zone melting techniques,&apos;-&apos; zones were usually caused to move by changing the position or temperature of a heat source, in the present technique a zone is made to move by impressing a temperature gradient across it. For example, a thin layer of molten A1-Si alloy, sandwiched between two silicon slabs having a temperature gradient normal to the layer, will travel through the hotter slab. One feature of temperature gradient zone melting, as this technique will be called here, is that zones of unusually small dimensions can be maintained. This leads to such diverse uses as have been listed in the abstract. In this paper fundamentals of the movement of a molten zone in a temperature gradient, and some practical applications thereof, are outlined. Assumptions The movement of a molten zone through a solid body of solvent substance in which a temperature gradient exists will be discussed. The length of the zone will be its dimension in the direction of motion. The direction of the temperature gradient will be toward the region of higher temperature. To be considered is a binary or higher order solute-solvent system in which the concentration of solute in the molten zone is sufficient to produce a lowering of the freezing temperature of the solvent which is at least of the order of the temperature range impressed on the charge. While we discuss primarily molten zones in a solid matrix, the principles are applicable to solid or vaporous zones in a solid matrix, a requirement being that the diffusivity in the zone be substantially greater than in the matrix. Diffusion of solute into the surrounding solid will be assumed negligible. In general, its presence will not basically alter the conclusions to be drawn. For illustration, a system represented by the partial constitutional diagram of Fig. la will be discussed, in which k, the distribution coefficient defined in the figure, is constant and less than unity. However, the technique is applicable to any solute- solvent system in which one component lowers the melting point of another component. Movement of a Molten Zone in a Temperature Gradient Consider, in the system AB of Fig. 1, where B is designated the solute and A the solvent, the effect of sandwiching a thin layer of solid B between blocks of solid A and placing the whole in a temperature gradient such that the temperature of the layer is above the lowest melting temperature of the system. Surrounded by an excess of A, the layer will dissolve A, becoming molten, and expand in length." As so- lution of A continues, at both interfaces, the mean solute concentration in the zone will move to the right in Fig. la, until at temperature T, the liquid at the cooler interface reaches the liquidus concentration C,. Solution of A thereupon ceases because the liquid T1 is saturated with A. The liquid at the hotter end of the zone, being at temperature T2, is not saturated with A at concentration C1. Hence solution of A continues there and concentration C2 is approached. A concentration gradient therefore is set up in the zone, causing A to diffuse toward the cool end and B toward the hot end. As a result, the liquid at the cool interface becomes supersaturated and a layer of crystalline A containing concentration kc, of B in solid solution freezes. Since a source of A

Jan 1, 1956

By T. L. Loucks, E. T. Guerrero

Pressure drop characteristics in a system composed of two adjacent concentric regions of different permeability were studied. The differential equations for continuity of mass flow in the two regions were solved using the Laplace transformation and the necessary boundary conditions to give the pressure distribution in the composite reservoir, the resulting equation for pressure drop at the inner boundary was evaluated for a variety of composite reservoirs and compared with the results for a uniform reservoir. From this study it was found that under certain conditions the permeability in both zones, as well as the size of the inner zone, can be determined from the pressure drop curve. INTRODUCTION The theory for the pressure distribution and pressure build-up behavior of a well producing a single, slightly compressible fluid from infinite and finite homogeneous reservoirs was presented by Hornerl and Miller, Dyes and Hutchinson.2 Extensions on this original work to provide improved and extended interpretations and better agreement between theory and observed results have been made by Matthews, et a1,3 van Everdingen,4 Gladfelter, et al5 Stegemeierand Matthews,6 Hurst and Guerrero,7 and Perrine.8 More recently Lefkovits, et al,9 studied pressure build-up behavior in bounded reservoirs composed of stratified layers. Houpeurtl0 has suggested various approaches to the general problem of variable permeability and porosity but presented no analytic solutions for particular permeability variations. Albert, Jaisson and Marionll studied the finite composite reservoir and presented numerical solutions to the unsteady-state case and an analytical solution valid only for large times. They also studied the so-called pseudo-steady state for several examples of radial permeability variations. Very similar examples have been treated in the unsteady state with application to pressure build-up by Loucks in an unpublished manuscript. More recently Hurst12 has presented the complete point-sink solution (valid for all times) for the infinite composite reservoir. He applied these solutions to interference between oil fields along with an even more elegant application of his explicit solution to the material-balance equation including water influx. Mortada 13 approaches the same application by avoiding the point-source limitation but gives the solution for the aquifer region which is valid only for large times. Hopkinson, Natanson and Temple14 have treated both the finite and infinite composite reservoir obtaining the pressure distribution for the inner zone valid for large times. This paper presents a theoretical study of the pressure distribution in an infinite composite reservoir composed of two adjacent concentric regions of different permeability. The object was to determine the manner in which pressure drop at the inner boundary of a composite reservoir depends upon time, the permeability of each zone and the size of the inner zone. Expressions for the pressure distribution in both zones are developed which take into account the radius of the sink and are valid for small times as well as large times. It was felt that an understanding of the pressure drop behavior in various composite reservoirs would be of assistance in the interpretation of some pressure build-up curves which do not behave according to the theory derived for uniform systems. Often the region surrounding the wellbore is either more permeable or less permeable than the reservoir because of the various drilling and completion practices. The effects of reduced permeability due to drilling-fluid invasion and of increased permeability due to fracturing or acidizing need to be more carefully defined. Therefore, an equation for the pressure drop in a composite reservoir was developed, and the effects of both the permeability in each zone and the size of the inner zone were studied. STATEMENT AND SOLUTION OF PROBLEM BOUNDARY CONDITIONS AND ASSUMPTIONS The physical system studied was a composite

By G. F. Comstock

A serious disagreement as to the effect of titanium on the hardenability of steel exists in published references to this subject. Kramer, Hafner and Toleman reported1 that acid-soluble titanium decreased the hardenability, with multiplying factors less than unity according to Grossmann&apos;s system for calculating hardenability from the composition. Crafts and Lamont, on the other hand, showed2 how titanium increased the hardenability, with multiplying fdctors up to nearly I.; for about 0.1 per cent titanium, though reducing the hardenability with higher titanium. Their data, however, were obtained almost exclusively from steels containing more than 1.4 per cent manganese, and thus should be considered as applying mainly to manganese steels. Likewise, the results of Kramer, Hafner and Toleman regarding titanium are subject to the limitation that although they eliminated the effect of the insoluble titanium compounds from their calculations, they did not make a similar correc- tion for the carbon that was combined with titanium and therefore occurred in a similarly ineffective form. It is suggested by the literature referred to that titanium may have different effects on hardenability, depending on the mode of its occurrence in the steel. The different effects on strength, ductility, etc., have already been discussed by the author.3 In the present discussion some comparisons, on the basis of hardenability as revealed by the Jominy end-quench test, are given between three titanium and two non-titanium steels heat-treated in the same ways, and between other titanium steels heat-treated in several different ways. Comparison of Plain-carbon, Vanadium and Titanium Steels The five steels used for these experiments were cominercially melted and rolled products received in the form of 1.5-in. rounds from three different mills. Their analyses are given in Table I. Steels 2, 3, and 4 are from the same basic electric heat1 containing 0.009 per cent of phosphorus and the same amount of sulphur. They were made by adding aluminum and low-carbon ferrotitanium to different ingots. No. I is a plain carbon

Jan 1, 1947