Search Documents

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- [ ] duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. [ ] The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. , I). Above the sand rock an overburden of Joachim limestone appears, which, thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes, where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OT THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By R. E. Gilchrist, R. F. Nielsen

When a gas is displaced by mother in a porous medium, and there is a relative immobile liquid present. there is a transition zone in which the gas composition varies from essentially that of the original gas to that of the injected gas. The change in extent of this zone with time may be governed by a mixing process in the direction of flow and by the rate of establishment of gas-liquid equilibrium, if the gases are appreciably soluble in the liquid. The relative importance of these two factors in deterri~ining the growth of the transition zone is discussed, with appropriate equations and experimental data. INTRODUCTION The various solution methods of oil recovery involve a transfer of the components of a mixture, whether within a single phase or between a liquid and gas. The similarity of a natural porous medium to systems used in separation and chromatographic processes makes it seem reasonable that certain concepts used by chemical engineers in "mass transfer" might be applicable to petroleum reservoirs. One approach, the HETP (height equivalent to a theoretical plate), involves a distance or length of time over which equilibrium might be con. sidered as established. Another approach involves direct use of a rate of mixing or rate of establishment of equilibrium. The latter approach has been preferred in relation to production problems. DISCUSSION AND PROCEDURE When a gas or liquid in a porous medium is displaced by one of different composition but miscible with it there will be set up a transition zone in which the composition varies from cssentially that of the original fluid to essentially that of the injected fluid. If the fluid being displaced is a gas, and there is a relatively immobile liquid present, the transition zone may be

By C. Feng, C. Elbaum

Knoop hardness measurements were carried out on large grains of iodide titanium containing different amounts of oxygen. For each oxygen content the hardness is recorded ainingas a function of the crystal orientation and of the angle 4 between the indenter diagonal and the projection of the C (hexad) axis in the surface. The results can be expressed by the following relation; hardness = n-k cos 2ø, where n and k are constants for a given oxygen content and crystal surface orientation. A NISOTROPY of hardness is a well-known phe-nomenon and has been reported for many metals.1-3 At the present time, however, such information is not available in the literature for titanium. Consequently, a systematic study of the simultaneous effects of oxygen content and crystallographic orientation on the hardness of titanium was undertaken in this laboratory. Evaluations of oxygen content in titanium are frequently carried out through hardness tests. Although such procedures may be justified in small grain specimens, the results of the present investigation indicate that the anisotropy of hardness should be taken into account in the case of coarsegrained specimens as well as in the case of pronounced preferred orientation. Materials and Experimental Procedures Iodide titanium, 99.99 pet pure and containing of the order of 0.002 wt pet O, was used throughout this investigation. The metal was arc melted in an argon atmosphere and cold rolled into strips 1/16 in. thick. These strips were subsequently recrystal-lized and strain annealed in vacuum (10" mm Hg or better) at 850°C in order to produce crystals varying in diameter from 10 to 25 mm. Oxygen was introduced into selected large crystals by heating at 700°C in an atmosphere of pure oxygen under an observed pressure of approximately 50 mm Hg. Each sample was subsequently annealed in vacuum at 850°C for 100 hr, in order to homogenize the oxygen content throughout the specimen. It was found that longer annealing was not necessary, for no change of surface hardness in a given direction was detected after prolonged annealing. The oxygen content was determined by the difference in weight of the specimens before and after the oxidation-annealing cycle. The accuracy of oxygen determination is within ±0.1 mg in samples weighing 0.5 to 1 g. A vacuum fusion analysis of oxygen was performed on several samples and gave results in good agreement with the ones obtained by the weight change. It should be emphasized that expected weight losses through evaporation of the metal in vacuum at 850°C' are many orders of magnitude lower than the precision of these measurements. Following the annealing treatment, both oxidized and unoxidized crystals were carefully polished. All detectable traces of surface cold working were removed by repeated polishing and etching. Laue back reflection X-ray patterns were taken for each crystal for the purpose of determining the orientation and ascertaining the absence of substructures detectable by this method. Hardness measurements, using a 1 kg load, were subsequently carried out on a Tukon hardness tester equipped with a Knoop indenter. The Knoop indenter was used throughout this work because indentations obtained by means of a Vickers indenter are considerably distorted due to the anisotropy of the elastic constants in titanium. Such distortions are much less pronounced in the case of Knoop indentations, although for some orientations a cer-

Jan 1, 1959

By F. W. Bowdish

A theoretical and experimental laboratory study has shown that the rate of breaking of oversized particles in a ball mill is proportional to 1) the concentration of such particles, and 2) the area of the balls, provided that the balls are larger than a certain size relative to the particles. If all undersized material were removed as formed, the rate of breaking would be almost independent of the quantity in the mill. Rate equations are given which are similar to those for zero, first, and second order reactions. Deviations of small balls from the equation for a second order phenomena are quantified by a factor called "nipping efficiency." Some data are correlated by a dimension-less equation, which is used to estimate nipping efficiencies from data not in the correlation. The investigation described here was undertaken after a literature survey revealed that little was known concerning the mechanism of breaking of particles within a ball mill and the effect of this mechanism upon grinding rates. One paper, by Roberts1 , offered a theory concerning the mechanism of breaking, and a rate equation for the breaking of particles larger than some size to particles smaller than that size. That paper provided the starting point for a theoretical and experimental investigation of grinding under carefully controlled conditions. THEORETICAL CONSIDERATIONS In his paper on the probability theory of ball mill grinding, Roberts theorized that "... a given expenditure of power leads either to a certain number of point to point blows per bp-hr or to a certain distance of line contact per hp-hr ..." He assumed that the balls touch each other during each blow or during moving contact. Then he said that a volume of pulp, dependent upon the size being considered, would be covered per minute within which all oversized particles would be crushed to particles smaller than that size. Naturally, the higher the concentration of oversized particles in the pulp, the higher the rate of which they would be broken. From this reasoning Roberts obtained the differential equation -dC/dt = k hp/ton C (1) where k is a constant for any size of particle, density of particle, and moisture content of pulp. C is the percentage of oversize in the material to be ground, t is the time, and hp/ton is the power input per ton of material in the mill. He then integrated the equation to log Co/Ct = k/2.3 hp/ton t , where Co and Ct are the percentage of oversize at time zero and t respectively. By always using the same quantity of material in a mill and assuming that it required constant power to run the mill, he was able to combine the horsepower per ton factor with the other constants to give an equation for a first order rate.

Jan 1, 1961

By J. M. Weehuizen

Complete details are given of the drilling method by which two shafts were sunk at the new Beatm'x mine of Staatsmijnen in the Netherlands. The nature of the rock strata in the Dutch mining district determined choice of the drilling rather than the freezing method. Data for each step and details of the equipment used are given in the illustrations. Staatsmijnen was founded in 1902 with government financial backing, but it is run as a private enterprise, on a commercial basis, with the normal fiscal obligations. The company now has four mines in operation with annual outputs amounting to 7 1/2 million tons of coal. In 1952 it was determined that a new mine—the Beatrix—would be opened. Details of the shaft-sinking operation are described in this paper. SHAFT LOCATION The coal-bearing carboniferous rock in the Dutch mining district is overlain almost completely by soft water-bearing strata, which at the site of the new shafts are about 1600 ft thick. The sinking of the new shafts through this soft water-bearing overburden (Fig. 1) is a costly and time-consuming affair. From the two availaible sinking methods: 1) Poetsch's well known freezing method or 2) the drilling method of Honigmann-de Vooys, the latter was preferred, not only because of its relative cheapness, under the prevailing conditions, but primarily because by using the drilling process, a special type of shaft lining of steel, concrete, and bitumen could be used. The new shafts, located 330 ft apart, have an inner diameter of 18 ft, 4 1/2 in. The boreholes, which have a diameter of 25 ft and which were drilled through nearly 1600 ft of overburden and some 100 ft of carboniferous, each contain more than 29,000 cu yd—by far the largest in the world. DRILLING METHOD The drilling method is based on the use of mud-flush—a thin mixture of clay and water—to keep the borehole filled during the entire drilling period and during insertion of the lining (Fig. 2). The pressure of the mudflush against the borehole wall is greater than that of the water in the surrounding

Jan 1, 1961

Jan 1, 1970

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

THE 125th meeting of the Institute was held in New York, Feb. 20-23, 1922, inclusive, and was the most successful annual meeting of the Institute ever held; there was a larger registration, there were more sessions of importance, and a greater number of sessions, than in any previous year. The total registration was 1331, comprising 351 New York members, 393 visiting members and 587 guests. At the annual business meeting of the Institute, held on Tuesday, Feb. 21, with President Ludlow presiding, there was a much larger attendance than usual. The report of the tellers was read and the following officers were declared elected: Arthur S. Dwight, Director and President-District 0 J. V. W. Reynders, Director and Vice-president-District 0 A. R. Ledoux, Director and Vice-president-District 0 Charles F. Rand. Director-District 0 George D. Barron, Director-District 0 William H. Bassett, Director-District 1 Thomas B. Stearns, Director-District 8 William Kelly, Director-District 5

Jan 3, 1922

By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

By G. F. Butterworth

The metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to, produce in the stock a physical condition having the requisite properties. The fist group consists of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat treated by giving it a quench and a draw. These barrels will be referred to as " heat-treated " barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent, of manganese, show a single very pronounced point between 1300" and 1350" F. (704" and 732" C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure shown in Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under a low magnification appears almost homogeneous, as in the case of fine grains of pepper and salt well mixed together, Fig. 6. This structure is substantially the same for all

Jan 1, 1920

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

Trans. No. Place Date Vol. Page 1. Wilkes-Barre Pa......May.71 1 3 2. Bethlehem, Pa.........Aug., '71 I 10 3. Troy, N.Y............Nov..: 71 1 13 4. Philadelphia, Pa........Feb., 72.. 1 17 5. New York. N. Y.*......May, '72.. 1 20 6. Pittsburgh. Pa.........Oct..' 72.. 1 25 7. Boston, Mesa..........Feb., '73.. 1 28 8. Philadelhia, Pa.*......May, '73.. 2 3 9. Easton, is............Oct..' 73.. 2 7 10. New York, N. Y.......Feb..' 74 . . 2 11 11. St. Louie. Mo.*........May,' 74 . . 3 3 12. Hazleton, Pa...........Oct., '74.. 3 8 13. New Haven Conn......Feb., '75.. 3 15 14. Dover,N.J.*..........May, 75.. 4 3 15. Cleveland,O...........Oct. 75. 4 0 16. Washington D. C......Feb.'' 76.: 4 18 17. philadelphia, Pa.......June,: 76.. 5 3 18. Philadelphia Pa........Oct 76.. 5 19 19. New York, N. Y.......Feb: '77.. 5 27 20. Wilkes-Barre. Pa.*.....Mag :77.. 0 3 21. Amenia N. Y..........Oct. 77.. 6 10 22. Philadeiphia Pa........Feb.;' 78. . 6 18 23. Chattanooga' Term.*. . . May' 78. . 7 3 24. Lake George: N. Y....: Oct. 78. . 7 103 25. Baltimore, Md.*.......Feb:' 79.. 7 217 26. ~ittsburgi, Pa.........~a;' 79.. 6 3 27. Montreal, Canada......~ept.;' 79.. 8 121 28. New York, N. Y.*......Feb., '80.. 8 275 29. Lake Superior, Mich....Aug., '80. . 9 1 30. Philadelphia, Pa.*......Feb., '81. 9 275 31. Staunton, Va..........May, '81. .10 1 32. Harrisburg, Pa.........Oct.. '81..10 119 33. Washington, I). C.*....Feb., '82. . 10 226 34. Denver. Colo..........Aug.. '82. . ll 1 35. Boston. Mass.*.........Feb.. '83..11 217 38. Roanoke, Va...........June, '83.. 12 3 37. Troy, N. Y...........Oct.. '83. .12 175 38. Cincinnati. O.*.... Feb, '84..12 4 39. Chicago Ill............May, '84. . 13 1 40. philadelphia, Pa........Sept., '84. . 13 285 41. New York, N. Y.*......Feb., '85. . 13 586 42. Chattanooga, Tenn.....May, '85..14 1 43. Halifax, N. S..........Sept., '85.. 14 307 44. Pittsburgh, Pa.*........Feb.. '86 . . 14 587 45. Bethlehem. Pa.........May, '86 .. 15 Ixiii. 46. St. Louis, Mo..........Oct, 86.. 15 Ixx. 47. Scranton, Pa.*.........Feb.', '87. . 15 lxxvi 48. Utah and Montana.....July '87.. 16 xvii. 49. Duluth, Minn...........July' '87. -16 xxiv. 50. Boston. Mass.*.........Feb.: '88. . 16 xxviii. 51. Birmingham, Ala.......May, '88. .17 xix. 52. Buffalo N. Y..........Oct. '88.. 17 xxiv. 53. New york, N.Y........feb.' ;89 . . 17 xxxi. 54. Colorado..............June' 89 . . 18 xvii. 55. Ottawa, Canada........Oct., 89. . 18 xxiv. 56. Washington, I). C.*. . . Feb. 90. .18 xxx. 57. New York, N. Y........sept:, '93. .19 vii. 58. New York, N. Y.*......Feb. '91. . 19 xxv. 59. Cleveland, O.......... June, :91 . .a xvi. 60. Glen Summit, Pa.......Oct, 111. . 20 lxi. 61. Baltimore, Md.*.......Feb.: '92. .21 xix. 62. Plattsburg, N. Y.......June, '02. . 21 xxxiii. 03. Reading. Pa...........Oct., :92. .21 xliv. 64. Montreal. Canada*.....Feb. 93..21 65. Chicago, Ill............aug.: '93..22 XI. 66. Virginia Reach. Va.*. ...Feb., '04. .24 xwl. 67. Bridgeport Coon.......Oct., '94..24 xxx?. 08. Florida ...'............Mar., '95. .25 xix 69 Atlanta. Ga......... Oct 95. 25 xi 70. Pittsburgh. Pa.*........Feb., '96.. 26 xvii. Trans. No. Place Date Vol. Page 71. Colorado..............Sept. '96. .26 xxix. 72. Chicago, Ill............Feb.. "97.. 27 xvii. 73. Lake Superior..........July '97. .27 xxx. 74. Atlantic City, N. J.*. ..Feb.: :98. .28 xvii. 75. Buffalo N. Y..........Oct. 08. .28 XXXVI. 76. New York,N. Y.*......Feb.: '99. .29 xvii. 77. California.............Sept., ;99. . 29 xlix. 78. Washington, D. C.*.....Feb., 00. .30 xix. 79. Canada...............Aug.. '00. .30 xlv. 80. Richmond. Va.*........Feb.. '01. . 31 xix. 81. Mexico................Nov..'01.. 32 cxviii. 82. Philadelphia Pa. $......May, :02. . 33 xxxv. 83. New Haven, Conn......Oct.. 02.. 33 xlvii. 84. Albany N. Y.*........Feb '03. .34 xxiii. 85. New York, N. Y........Oct.': '03. .34 xi. 86. Atlantic City. N. J.*....Feb., '04. .35 XXIII. 87. Lake Superior..........Sept.'04. .35 dii. 88. Washington. D. C......May' '05. .36 xlii. 89. British Columbia.......July, '05. . 36 90. Bethlehem. Pa.........Feb. '06. .37 xli. 91. London, England.......July: '06. .37 xlviii. 92. New York, N. Y........April, '07. . 38 lii. 93. Toronto, Canada.......July. '07. .38 lix. 94. New York, N. Y........Feb., :08. .39 xli. 95. Chattanooga, Tenn.....Oct.. 08..39 xlviii. 06. New Haven Conn......Feb. '09. .40 xli. 97. Spokane,Wash.........Sept:.'09. .40 xlviii. 98. Pittsburgh, Pa.........Mar.,'10. .41 xxxviii. 99. Canal Zone............Nov.,'10. .41 dv. 100. Wilkes-Barre, Pa.......June. ' 11. . 42 xxxiv. 101. San Francisco, Cal......Oct.. '11..42 xliv. 102. New York. N. Y.*......Feb 12. .43 Ixxvii. 103. Cleveland, Ohio........0ct;' '12.. 44 wii. 104. New York, N. Y.*......Feb.. '13. .45 xv. 105. Butte, Mont...........Aug., '13. .46 ?' 108. New York, N. Y........Oct., 13..47 vii 107. New York. N. Y.*......Feb.. '14..48 xv. 108 Salt Lake City. Otah Aug. :l. 49 5: 109. Pittsburgh, Pa.........Oct., 14. .50 vii. 110. New York, N. Y.*......Feb., '15. .51 xvi. 111. San Francisco, Cal......Sept., '15. .52 xii. 112. New York,N. Y.*......Feb., '16..54 xvi. 1 Arizona...............Sept.,'l6. .55 VII 114. New York, N. Y.*......Feb., '17: .56 vii. 115. St. Louis, Mo..........Oct.. '17..57 vii. 116. NewYork,N. Y.*......Feb.. '18..59 xvii 117. Colorado.....:........Sept.,'18. .60 vii. 118. Milwaukee, Wis........Oct.. '18. .60 x:!: 119. NewYork,N. Y.*......Feb., '19..61 xi. 120. Chicago...............Sept.,' l9.. 62 VII. 121. New York, N. T.*......Feb., '20..63 ix. 122. Lake Superior District. .Aug., '20.. 66 ix. 123. New York, N. Y.*......Feb., '21. .66 xiii. 124. Wilkes-Barre, Pa...... Sept.. : 21.. 66 xix. 125. New York, N. Y.*......Feb., 22. .67 ix. 126. San Francisco. Cal......Sept.,:22. .68 xxix. 127. New York, N.Y.*.....Feb., 23. .69 xxix 128. Canada...............Aug., '23. .69 xxxv! 128.129. New York, N. Y.*......Feb., ;24. .70 xxxi. 130. Birmingham, Ala.......Oct. 24. .71 xxxiii 131. NewYork.N Y.*......Feb.: '25.. 71 xxxviii. 132. 131.Salt Lake City, Utah .. .Sept., '25. .73 xvi 133. New York, N. Y.*......Feb., '26. .73 xxii. 134. Pittsburgh Pa ....... Oct.. '26. .74 xv. 135. New York,' N. Y.*............Feb., '27. .75 x::: 135.136. NewYork,N. Y.*......Feb., '28..76 104 137 NewYork.N. Y.*......Feb., '29. .291 116 138.San FranciscoYork,N.Y. Cal..........Oct. 29..308 406 139. New York, N. Y.*...Feb., '30..30H 1321

Jan 1, 1930

By Gorr W. W., Wyche E. H, R. Smith

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By Gorr W. W., R. Smith, Wyche E. H

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947