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By H. F. Beeghly

UNTIL recently the only criteria by which steels were judged were their cost and their mechanical, chemical, and physical properties. The user was concerned with such properties as corrosion resistance, tensile strength, response to thermal treatment, hardness, ductility, and, to a growing extent in recent years, with behavior at high temperature. As plans were made to build power reactors, a new set of properties became important—the nuclear characteristics, which had to be considered by the designer and engineer in building his plant. The nuclear engineer developed methods for the rare and new metals and produced them in high purity, often at great expense. The pure metals then provided the raw materials for tailor-made alloys. For more common structural metals, such as steel, the nuclear industry depended on commercially available materials. Generally, the quantities required were small and specifications were rigid. It is not surprising, therefore, that difficulty was frequently encountered in procuring structural mate-

Jan 1, 1957

By C. W. Vaupell

THE Huitzuco mines lie in north central Guerrero, Mexico; production has been about 90,000 flasks of quicksilver since 1873. Near-surface ores fill extinct mud geysers and the deep deposits are chambered veins, stock-works in brecciated blocks, and replacements in limestone. The epigenetic minerals livingstonite, stibnite and sulphur occur in limestone, gypsum and dolomite through a developed vertical range of 260 meters. The deepest workings expose an increased amount of stibnite, which probably indicates that the lower limit of mercury mineralization is being approached. A resurgence of heat and water formed geysers over an extended area after the period of mercury mineralization. Mud geysers, which are situated, in the outcrops, contain the secondary mercury minerals, cinnabar and barcenite in the gravel and mud filling the vents. A 150-ton flotation plant is in operation concentrating stope fills that assay 3.0 kg. of mercury per ton. In one open stope, which is more than one hectare in area and 60 m. high, 150,000 tons are available. INTRODUCTION The Huitzuco mercury mines are of interest because of the unusual occurrence of ore in extinct geyser vents and the presence of several rare mercury minerals. Some of the deposits have typical characteristics of the telethermal zone and there is a gradation towards typical epithermal mineralization in depth. Halse,1 Villarello,2 Mactear3 and Merrill4 have described the geology and the early operations in the district, and Barcena5 and Mallet6 have described the rare mercury minerals, livingstonite and barcenite, found at Huitzuco. LOCATION The village of Huitzuco lies in the north central part of the State of Guerrero, Mexico, 27 km. (16.7 miles) east of Iguala, which is the largest and most important town in the area. Iguala is served by the Mexican National Railways and also by the Mexico City-Acapulco highway. The highway is surfaced from Mexico City to Iguala, a distance of 200 km. (124 miles) by road, and there is a fairly good, level, dirt road from Iguala to Huitzuco. The elevation above sea level is about 1000 m. (3280 ft.). The climate is warm and very dry except during the rainy season, from June to

Jan 1, 1937

By F. F. Frick, Frederick Laist

In a leaching process, having obtained the copper in solution, the choice of the precipitation method is influenced by the following factors: 1. Availability of precipitant. 2. Adaptability to the leaching process. 3. Final product desired. 4. Regeneration of leaching solutions. 5. Fouling of solutions. There are three general classes of precipitation methods: 1. The use of iron, scrap or sponge. 2. Electrolytic deposition. 3. The use of some gas or reagent by which the copper is obtained, usually in the form of an intermediate precipitate which requires further treatment. For example, the precipitation of, the copper as Cu2Cl2 from chloride solutions; with SO2 gas. The use of iron is adapted to almost any process. It has the great advantage of extreme simplicity, and the recovery of the copper and any values present in a highly concentrated, easily treatable form. The disadvantages are the cost in isolated places, the uncertainty of the scrap-iron market, and the fouling of the leaching solutions. The latter is a serious factor, when a reagent such as salt is used in them, which makes necessary their re-use. Where applicable, electrolytic deposition is very attractive. The copper is obtained in a form directly marketable, there is a regeneration of acid and no fouling of solutions. Unfortunately, chloride solutions do not lend themselves to electrolysis. An entirely satisfactory anode material has not yet been discovered, although magnetite, apart from being rather brittle, seems to answer the requirements fairly well. The use of a method of the. third class is involved in many special

Jan 1, 1915

By Edward Sampson, Allan B. Griggs

Surveying of many holes drilled by the U. S. Bureau of Mines in the Metaline district has shown surprising deviations. The holes start in the Ledbetter slate (Ordovician) and pass into the underlying gently dipping Metaline limestone (Cambrian) at varying depths, locally in excess of 1000 it. All holes start vertical, but one had deflected as much as 35° at a depth of only 300 it. One hole was found to be deflected 70' at a depth of 1000 ft. These deviations were not indicated to the drillers by any action of the rods or machines. Analysis of the survey data in the light of the observed geology indicates that the holes deviate most in the Ledbetter slate and scarcely at all in the Metaline limestone. The upper part of the "limestone'" in most holes is a massive rock strongly altered by hydrothermal action and essentially homogeneous. The slate is only obscurely bedded but has a cleavage, varying from slight to strong, which is unrelated to bedding. Drill holes have deflected to become nearly perpendicular to the cleavage. Several plans and cross sections are submitted showing the behavior of various holes. Introduction The Metaline district of northeastern Washington has received much attention recently and has promise of becoming even more important as a source of zinc than at present. Exploration has been conducted largely by deep diamond drilling, and in the course of this work it was found that holes became seriously deflected. This paper deals with the nature and causes of these deflections. The district lies along the Pend Oreille River in the northeastern corner of Washington, about loo miles north of Spokane, 9 miles from British Columbia, and 15 miles from Idaho. Three mines are now in operation and for a number of years have furnished a considerable production of zinc and lead. The ore contains zinc and lead in a ratio of about 31/2 to I, and occurs in the upper part of the Metaline limestone of Cambrian age, the upper member of which, where unaltered, is a rather pure limestone. This is overlain by Ledbetter slate of Ordovician age. Ore has formed by replacement of limestone, commonly 100 to 200 ft. below the slate, in areas of gentle dip, resulting in extensive tabular ore bodies. In and near ore, limestone has been intensely altered to granular dolomite and fine-grained quartz, which, where it predominates, forms "jasperoid." As part of their war program, the Geological survey and Bureau of Mines of the U. S. Department of Interior have been cooperating in an investigation of the district. The exploration by the Bureau of Mines in 1943 and 1944 was conducted largely by deep diamond drilling in which as much as 1000 ft. or more of Ledbetter slate was penetrated before the ore-bearing Metalin-2 limestone was reached. During the course of this drilling it was found that holes were seriously deflected while traversing the Ledbetter slate.

Jan 1, 1949

By A. J. Teplitz, J. K. Rodgers, E. M. Pohoriles

This note is presented in order to call attention to a newly developed laboratory apparatus that appears to have interesting possibilities for the study of lost circulation of the pressure-parting type, for a more realistic evaluation of sealing materials for this type of loss, and for investigation of other aspects of hydraulic fracturing. A study of lost circulation, conducted jointly by operating divisions of the Gulf Oil Corp. and the Gulf Research & Development Co., has been in progress for the past few years. Earlier phases of the study dealt with mechanical factors contributing to loss of returns in laminar type sediments.' One aspect of this type of loss which has been widely discussed in the literature and elsewhere concerns the geometry of the fractures into which such losses occur. This subject is not merely a philosophical one, but has an important bearing on procedures for combating lost circulation difficulties and on other well operations. The further course of the collaborative studies previously mentioned has produced some information on this subject which, though limited in amount, is believed to be significant. In several typical cases of lost circulation in laminated shale and sand formations, the wells have been surveyed with instruments2,3 capable of detecting the points of loss with considerable accuracy. These wells were located in the Gulf Coast of Texas and Louisiana, in the Texas Panhandle, and in the Rocky Mountain area. In each of these instances the loss was shown to be occurring at some distance removed from the bottom of the hole and sharply confined to a very narrow interval, less than 1 ft in thickness. It is rather difficult to imagine that fractures of a vertical nature' would be of the limited extent indicated by the surveys in these wells. Furthermore, the high rates of loss at relatively low pressure differentials observed in some of these instances together with the narrow intervals involved would appear to require the radial flow pattern which would be associated with a more or less horizontal fracture plane. In view of the foregoing observations and records of successful squeeze cementing operations, in attempting to construct a laboratory apparatus For simulating pressure induced lost circulation, it was decided that the design should be based on a horizontal type of fracture. It was realized that5,6 Vhe production of horizontal fractures in a formation with non-penetrating fluid requires some mechanism for transmitting vertical components of the hydraulic forces to the plane of parting. This was accomplished, as will be evident in the description of the apparatus that follows, by providing recesses in the wall of the borehole which are believed to be representative of wellbore configuration found in Gulf Coast wells. The possible influence of such borehole irregularities on both pressure fracturing and the treatment of lost circulation appears to have been neglected in many studies of these subjects. It is believed that the present apparatus, incorporating features that take into account some of the factors mentioned, will provide means of gaining a further understanding of pressure induced fracturing and possibly for more realistically evaluating the numerous sealing agents, particularly the non-time-setting materials employed in treating the pressure-parting type of loss. DESCRIPTION OF APPARATUS The test cell used in the laboratory investigations is shown in Fig. 1. A schematic diagram of the entire system is shown in Fig. 2.

Jan 1, 1956

By H. R. Stahi

THE ore of the Southeast Missouri lead district consists essentially of galena in dolomitic limestone. The galena usually is in a very finely disseminated condition. The experience of recent years in the concentrating plants of the St. Joseph Lead Co. has shown that dry crushing carried to a point where about 90 per cent of the ore passes a 14-mesh screen liberates the larger portion of the galena, and minimizes further necessary reduction in rod or ball mills. Concentration practice has attempted to carry size reduction to a point where economic unlocking of the galena is obtained, without causing undue sliming of the very friable galena. While 60 per cent of the tonnage of the district is treated by the flotation process, only 40 per cent of the total concentrates is produced by that means, as efforts have always been made to keep the grade and tonnage of flotation feed as low as possible. The milling practice of the district for some years has recognized the generally accepted idea of better selective grinding in rod mills as compared with ball mills, with the attendant decrease in production of fines. The function of rod and ball mills in the various concentrating plants is the grinding of table middlings and coarse tailings that carry lead values too high to be discarded. The simplified flowsheet in Fig. I illustrates the place of grinding mills in the circuit. The arrangement of classifiers, tables and mills constitutes a closed circuit within somewhat flexible limits. In 1937 experiments were conducted in replacing the ball charge in a 6 by 4-ft. ball mill with rods 2 in. in diameter and 51 in. long. This step was taken with some hesitancy, as it was easy to picture a mass of tangled and crossed rods. However, no difficulties developed, and after a short trial period, six more ball mills were converted to rod mills. These mills are of the spur gear and pinion, belt-driven type, using in most cases a 75-hp. motor and having a 9 1/2 -in. open trunnion discharge. As ball mills, they carried a charge of 16,000 to 20,000 lb. of balls, 2 in. in original size. The feed to the mills was dewatered by dewatering wheels and introduced at 70 to 75 per cent solids, with a single scoop feeder. One change in mill design was found advisable when rods were introduced. The existing end liners had an outward flare of 3 ½ in. in 12 in. These were replaced by linings having vertical interior faces, in order to prevent undue end travel of the rods. This change gave an effective working length of 5 2 ¾ in. inside the mill. No alterations were made in the shell liners, which are of the smooth type, made of manganese steel 2 in. in original thickness. The rods at present in use are 51 in. long and 1 3/4in. in diameter. The composition has been varied at times; at present they contain 0.70 per cent carbon and 0.70 per cent manganese. Some breakage and etching occurs as the rods become small, but this is considered preferable to using softer rods, which may kink and cause tangling of the charge. The mill charges are renovated occasionally, broken pieces being removed and the charge brought up

Jan 1, 1945

By R. W. Parsons

wben a displacement front encounters an isolated permeability heterogeneity, it will be perturbed. The details of this perturbation will depend on the beterogeneity size and shape, the Permeability contrast, and the mobility ratio. This paper deals with the displacement front behavior for one, simple, mathematically tractable model: a circular permeability discontinuity and unit mobility ratio. The progress of an initially planar front is shown for four permeability contrasts: k2/k1 = 0, 5/2, 2, m. The front distortion is more pronounced than streamline and isopotential distortion and it approaches a constant shape downstream from the discontinuity. INTRODUCTION The impact of reservoir heterogeneities on oil displacing processes depends upon the variation of the heterogeneous property (frequency distribution), its disposition (spatial distribution), and the inherent stability of the displacement mechanism.l The interplay of these factors plus the impracticability, if not impossibility, of describing a natural rock system in any detail makes exact displacement front movements difficult to determine. It is useful, however, to be able to qualitatively visualize what heterogeneities will do to a displacement front. In this respect certain simple models that can be treated analytically are of value. The following analysis will show the displacement front behavior for one such model. MODEL DESCRIPTION The flow field is two-dimensional and infinite in extent. The fluid flow is single phase, steady state and unidirectional at x, y = 2 m, or before insertion of the discontinuity. A circular permea- bility discontinuity is placed at the origin. Porosity and thickness are the same within and exterior to the heterogeneity. This is exactly the same model that was used by Greenkorn et al. to check analytically Streamlines as determined by Heie-Shaw flow models and finite difference computer techniques.2 FRONT POSITION CALCULATIONS The results of displacement front calculations are presented in Figs. 1 through 4 for four different permeability contrasts: k2/kl = O, %, 2, m. The times corresponding to the front locations are the Same for the 0 and cases! and for the 1/2 and 2 cases. The determination of front positions at various times is based on known analytical expressions for velocity potentials ().2 and stream functions ().2 These expressions are in terms of the x and y

Jan 1, 1969

By J. S. Aronofsky, H. J. Ramey

Potentiometric model studies of the five-spot water flood to determine the influence of mobility ratio upon injection or production histories are described. The results suggest a method for the correlation of data from field pilot tests for the estimation of an effective mobility ratio and its effect upon field water floods. The effect of the well spacing-to-well radius ratio upon production histories is presented. A method of accounting for this factor is suggested. The influence of injection (or production) rates and injection and production well pressures upon production histories is shown. The five-spot well pattern was investigated for water-to-oil mobility ratios of 0.1 to infinity. INTRODUCTION It has been well established that mobility ratio has an important effect upon flood patterns.1,2,3,4,5 It should be equally apparent that injection and production histories must also be influenced by mobility ratio. However, none of the articles referred to above mention the importance of being able to predict the effect of well pressures (or injection rates) during the entire time history of a waterflood operation. A complete description of production histories (the terms "injection" and "production" are synonymous for the steady-state model under consideration) would provide values for well pressures and interface positions at any time for a specified injection rate. conversely, if the waterflood problem is specified in terms of a constant injection well pressure, then it would be desirable to know the injection rate and interface positions at any time. This paper describes the results of potentiometric model studies which were used to analyze the influence of mobility ratio on injection or production histories. A method is presented for calculating production histories over a range of ratios of well spacing-to-well radius. The basic method described in this paper to evaluate production histories is to: (1) determine interface position as given in Ref. 1, and (2) measure electrical current and voltage drop for each interface position. It should be mentioned that the current state of knowledge on flood patterns as affected by mobility ratio shows that significant discrepancies exist between the results of various investigators2,3,4,5. It is beyond the scope of this paper to discuss the reasons for such discrepancies. However, the method of determining production histories presented in this paper could be applied to any of the swept-area patterns presented in the literature. All results given in this paper are based on a set of swept areas obtained by the potentiometric method. Potentiometric analyzer technique is adequately described in the literature, but the basic assumptions involved in work of this nature bear repetition. It is assumed that: 1. A distinct oil-water interface exists in the reservoir; only water is mobile in the region behind the interface (water zone) and only oil is mobile in the region ahead of the interface (oil zone). 2. There is a fixed mobility value, (k/µ) w associated

Jan 1, 1957

By Irwin Roman

IN studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two components ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. General considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note I). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude Io with vertical component Vo and horizontal component H,. Six station points along a traverse' across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the' disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1946

By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By J. S. Ross

Although the opinion has prevailed for several years that bottoni-hole choking under certain flow conditions should effect an increase in flow efficiencies, the use of bottom-hole chokes until recently has been limited in application mainly because of mechanical difficulties encountered in their construction. Within the past year, however, bottom-hole choking, through the development of a removable type of choke, has been applied successfully under various conditions of flow in many Mid-Continent fields. The observation of these field tests indicates that bottom-hole choking, although not applicable to all flow conditions, has an important place in the operation of oil and gas wells. This paper gives briefly the conclusions drawn from the data obtained from the experiments with this bottom-hole choke under various flow conditions, and a description of the choke and its operation. Purpose of Bottom-hole Choking Since, in a normal well, the velocity with which the column of gas is moving generally has a direct bearing upon the quantity of oil it can lift, probably the main purpose of bottom-hole choking is to accomplish an increase in the velocity of this- rising column, particularly in the lower portion of the tubing string. This it does first, by expansion of the free gas accompanying the oil; next, by liberation and expansion of some of the occluded gas normally carried in the oil to the surface; and lastly, by atomization, which results in a more intimate and uniform mixture of the oil and gas. It is apparent, then, that if this velocity, particularly in the lower portion of the flow string, at a given rate of production, is inefficiently low, owing either to an insufficient supply of gas or to excessive surface choking, and slippage takes place, bottom-hole choking should bring about an increased velocity of the gas and hence an increased lifting capacity. But if the velocity of the column of gas at this same rate of production through a surface choke alone is at or above a velocity necessary to lift the oil efficiently, increasing the velocity by bottom-hole choking would probably serve no useful purpose, other than to steady the flow by the better mixture of oil and gas and to lower delivery pressures.

Jan 1, 1932

By C. M. Shigley

The record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.' The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 to 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000- ooo-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation—the largest known magnesium plant utilizing sea water as its raw matcrial. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and 7 miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1949

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By John S. Brown

As a part of a symposium on the relations of structure to ore deposition, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replacement deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifications, to mineralization in unmetamorphosed limestone. In metamorphosed formations, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might faeilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a finc-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a limestone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone is of little or no importance.

Jan 1, 1941

By J. C. Williams

THE operations described in this paper are those of the flotation plant of the Valley Forge Cement Co. at Conshohocken, Pa., and concern the use of a particular cationic reagent-namely, DP-243. The role of this reagent in this plant may be better understood by first considering the purpose of beneficiating cement rock in general and the specific problems at the Valley Forge plant. The ultimate purpose of beneficiating cement rock is to obtain a kiln feed of the desired chemical composition in a form suitable for the most efficient kiln operation. The chemical composition is governed by the type of cement to be made. Before government restrictions (the purpose of which is to simplify operations during wartime) limited the types of portland cement a manufacturer is permitted to produce, five principal types of cement were generally recognized by the industry. They are based upon chemical and physical specifications proposed by the American Society for Testing Materials, federal and other governmental agencies, state highway departments, water boards and other users of large quantities of cement. The physical as well as chemical specifications for any particular type of cement necessitate proper proportioning of the major components-that is, the silica, alumina, iron and lime-and it is necessary to establish and maintain definite limits for each in the raw mix. The manufacturer must then prepare a kiln feed of a composition that will yield a final product that will fulfill the desired specification. This step is further complicated for kilns using coal as fuel, by the amount and analysis of the ash introduced. The amount and nature of the dust lost during burning will also affect the composition of the kiln feed. The problem of preparing a kiln feed of the desired chemical composition is not a simple one, and it is the final product that governs the methods used to obtain such a feed. For example, in starting with a material deficient in lime for the mix sought, it may not be sufficient to raise it to the required lime content. The other constituents must also be present in the proper proportions. In some cases, it may be necessary to raise the lime content to a point greatly exceeding that of the final mix, then, by addition of one or more other materials lower in lime, obtain the mix. The rock used at the Valley Forge plant is a metamorphosed argillaceous limestone of the Jacksonburg formation, the same formation as that of the Lehigh Valley cement rock (which occurs approximately 50 miles north), and its oxide composition is similar to that of the latter. The only practical differences between the two are that, as a result of metamorphosis, crystallization of the Valley Forge rock is considerably coarser and it contains less carbon than the Lehigh Valley rock as well as slightly more magnesia in the form of magnesian mica. The calcium carbonate content of the various strata in the Valley Forge quarry ranges from about 65 per cent to over 85 per cent, the average for the entire quarry being somewhat under the requirement for manufacture of cement, which usually is from 75 to 76 per

Jan 1, 1946

By G. W. Maynard

In this paper I desire to embody the results of some personal observations of the working of the Siemens direct process as I witnessed it for a part of three days at the works of the Siemens-Anderson Company, in Pittsburgh. This preliminary investigation was to have been followed up by one extending over a considerable period of time, and would have embraced analytical and physical tests. Circumstances over which I had no control, resulting in the temporay suspension of work, have postponed the presentation of a complete paper. If the opportunity is afforded me, I purpose doing this at a future meeting of the Institute. To those interested in the development of the process, reference is made to the papers of Dr. Siemens in the Journal of the Iron and Steel Institute for the years 1873 and 1877, and to the paper of our late lamented brother, Holley, in the 8th volume of the Transactions of our owu Institute. Dr. Siemens, in the introduction to his paper "On the Manufacture of Iron and Steel by Direct Process," read before the Iron and Steel Institute in september, 1877, says: " In mixing comparatively rich iron ore in powder with about 25 per cent. of its weight of pounded coal, and in exposing this mixture for some hours to the heat of a common stove or of a smith's fire, metallic iron is formed, which, on being heated to the welding-point on the same smith's hearth, may be forged into a horseshoe of excellent quality. The admixture with the ore of some fluxiug materials, such as lime or clay, will, in most cases, be of advantage to rid the iron of adherent slog." This is the keynote of the Siemens direct process. Dr. Siemens says further: " If we regard the production of wrought iron from an abstract point of view, we perceive that we have to accomplish two things, viz., the deoxidation of the ore, arid the fusion of the earthy matter mixed with it; and if we calculate the amount of carbon necessary to accomplish this end, weshall rind that in using, say, hematite ore, consisting of peroxide of iron with from 10 to 15 per cent. of silica, we shall require barely 40 per cent. of carbonsceous matter per ton of iron contained in the ore to effect its reduction, and also the fusion of the slag."

Jan 1, 1882

By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick's law for a source of finite thickness.' For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By R. V. Higgins, A. J. Leighton

A fast method is needed for calculating thoroughly the performance of two-phase flobr~ in reservoir rock with complex geotrietry. The authors present such a method and .slzow its accuracy by romparison with laboratory performrrnce of a five-spot pattern. In making the performance c.alculations, the octant of the five-spot pattern was divided into four channels. The computer tinle required for the culculation was one rllinrcte. This is rorighly about minute per channel. INTRODUCTION By using an electronic computer it is now possible to make reservoir performance calculations in which fewer assumptions and more significant variables are included than was possible with a desk calculator. These performance calculations include such variables as the properties of the reservoir rock and its contained fluids, properties of the rock-fluid system and even different well-spacing patterns. Usually, the more variables that are included the higher the computer cost—and time on the computer is expensive. As a result, a short procedure is needed so the many variables will be included and accurate performance calculations will result. If a reservoir is composed of alternate layers of permeable and impervioi~s rock, and if each conducting layer has a different relative permeability, the combined computer cost for calculating each layer by the present long computer programs (which includes different well-spacing patterns and other variables) would be expensive. The performances of complex spacing patterns in a field often are studied by a potentiometric model, but in these model studies the analogy is to the flow of only a single phase. This paper presents a procedure to calculate the performance of a five-spot pattern with two phases flowing using a potentiometric model as a guide for the dimensions of channels and other related data. The time required to calculate the complete performance is about one minute on the IBM 7090 or four minutes on the IBM 704. The procedure can be extended to calculate the performance of more complex well spacings or an entire field with little modification. The procedure has been tested on the performance of the laboratory water floods of a five-spot pattern reported by Douglas, et alThe range of viscosity ratios in the laboratory experiments is from 0.083 to 754, which is extensive. The accuracy of the performance calculations is excellent as shown by the plotted points in Fig. I. The recovery as influenced by the geometry of the five-spot, taking into account the deviation from true radial character, has been predicted by Aronofsky and Ramey." The authors used a potentiometric model to determine the sweep efficiency to breakthrough of the flooding agent. Dyes, Caudle and Erickson,' by means of a laboratory model, show the influence of mobility ratio on recovery after breakthrough of the injected material. Dyes, et ai, used the X-ray shadowgraph technique and miscible phases in their studies. Craig, Geffen and Morse from the analysis of the performance of their laboratory model correlate many variables, including average saturation of a flooding agent determined by permeability relationship. Craig, et al, used X-ray shadowgraphs to determine the sweep efficiencies in sandstone models. In this report the sweep efficiency is not needed, and the important effect of continuously changing saturation gradients before and after breakthrough