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By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood' has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3'4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

By K. A. Slagle

Hydraulic analysis of the wellbore has become increasingly inzportant for designing cementing operations and selecting equipment, materials and techniques to complenzent modern well-c-ompletion practices. Non-Newtonian fluid technology has advanced beyond the point where former empirical methods of analysis adequately define the hydraulic system and fluid properties. In view of these factors, this paper describes a series of rheological calculations which have been found practical, through field usage, for assistance in selecting a cementing program. A relatively simple laboratory method using standard viscometric equipment is suggested for determination of the rheological properties of slurries, and clrrta are presented on some of the more common cementitrg conzposition.A. A criterion for divergence from laminar-flow characteristics has been proposed. Usefulness of the calculations is indicated by examples of cementing operations where they have been used. INTRODUCTION With the changing aspects of well-completion practices during the past few years, it has been increasingly important to have a relatively simple method of analyzing the flow conditions existing in the well during cementing operations. This is particularly true in view of the improved economics toward which most of the changes have been directed. Rheological characteristics of slurries used for cementing should be a major consideration in the trend toward smaller casing sizes, either single or multiple strings. Receiving increased attention is the practice advocated in 1948 by Howard and Clark' of attaining turbulent flow with the fluids circulated during a primary cementing operation. While there may still be a difference of opinion concerning this technique, most available information indicates that superior primary-cementing results are generally obtained when high displacement rates are employed. Fluid properties of the slurry to be used must be available, as well as calculation methods, to determine what flow rates should be attained and the probable consequences in terms of frictional pressure and horsepower utilization. It would certainly be inappropriate to attempt high displacement velocities if sufficient pressure might be developed to create lost circulation. Since cementing slurries are non-Newtonian fluids, it is not possible to define their rheological or fluid properties by the single factor of viscosity and then make calculations for the quantities just described. Because the shear stress-shear rate ratio is not constant: it becomes necessary to establish at least two parameters for adequate fluid-flow calculations. It is not the purpose of this paper to delve into the mathematical development of non-Newtonian technology, nor to discuss the arbitrary classification system under which a single fluid may resemble two or three different classes depending upon experimental conditions. Rather, the intention is to present a useful series of calculations based on a concept applicable to both Newtonian fluids and to the preponderance of non-Newtonian fluids encountered in the oil-producing industry. Development of this approach was begun some 32 years ago,' and has most recently been brought to fruition by Metzner and his co-workers at the U. of Deleware. Some non-Newtonian fluids encountered in the petroleum industry, other than cementing slurries, have also had the benefit of this method of analysis."' The two parameters required to define the fluid are usually denoted by the symbols n' and K' and, for the purposes of this discussion, are called "flow behavior index" and "consistency index", respectively. These two slurry properties permit calculation of the Reynolds' number and the "critical" velocity, or the velocity at which departure from laminar flow begins. EXPERIMENTAL DETERMINATIONS The two principal instruments used for rheological studies are the pipeline (capillary-tube) viscometer and the rotational viscometer. When conveniently possible, a capillary-tube viscometer (where the pressure drop and flow rate of the material can be measured) is the better method for rigorous determination of the flow behavior index and consistency index for non-Newtonian fluids. With pressure-drop data at various flow rates, it is then possible to prepare a logarithmic plot of shear rate as the abscissa-shear stress as the ordinate. For fluids which do not exhibit time-dependency, these data will usually produce a straight line. The flow behavior index n' represents the slope of this line, while the consistency index K' becomes the intercept of this line at unity shear rate in accordance with the mathematical derivations associated with this concept of rheology. Due to the difficulties anticipated in maintaining a uniform, pumpable cement slurry for the time interval required to obtain measurements from the pipe viscometer, the n' and K' data reported herein were obtained using a direct-indicating rotational viscometer (Fig. 2). The

By T. S. Lovering

The use of geothermal energy is expanding very rapidly. This type of energy has proven commercially profitable for generation of electricity, for space heating, process heating, auxiliary heating of water in conventional steam power plants and for recovery of chemicals contained in natural hot water and steam. Two types of geothermal energy sources are recognized: 1) hot springs in regions of nearly normal heat flow that tap a deep reservoir through which water moves slowly to a hot springs conduit and then rapidly to the surface; 2) hyperthermal areas in which the water is heated by a relatively concentrated heat source related to volcanicity. If there is a geologic trap that provides a geologic analog to a steam boiler, as at Larderello, Italy, the hyperthermal area will have a convecting system that develops superheated water at relatively shallow depth and may provide natural steam in large quantities. If a hyperthermal area is to be productive for a long time, the underflow into the reservoir should be slow enough to allow the heat source and convective system to heat the underflow to the working temperature, and the production rate must not exceed this rate of underflow. A model based on a typical aquifer suggests that the rate of movement of water through the reservoir be such that a few years are spent in transit between isotherms that are spaced about 2°F apart. The possibility of finding blind geothermal areas is illustrated by discussion of the techniques developed in evaluating the subsurface temperatures in the East Tintic district of Utah where a map of isotherms at water level (2000 to 2000 ft below the surface) shows that a hyperthermal area may exist a short distance southeast of the mining district. Very nearly all of the energy that man currently uses comes ultimately from the sun's radiation. This includes water power, fuels such as wood, peat, coal and petroleum, the wind and all our animal power. In the paper summarizing a conference on solar energyl6 the average amount of solar energy received daily on the earth is taken at about 1 cal per m2 per min or slightly less than 2 pcal per cm2 per sec; this is almost exactly the amount of energy on the average that the earth liberates in regions of normal geothermal gradient due to its own internal heating. In many places, however, the energy released is many times the average and in some of these hyperthermal areas, geothermal steam is used for generation of electricity, and hot springs are used for heating buildings and private dwellings, process heating, auxiliary heating of water in conventional steam power plants, and chemicals may be recoverable from both hot water and steam. The use of hot springs waters for heating houses goes back hundreds of years but until recently was confined to a few dwellings close to the hot springs. In Korea, some houses had hot spring water channeled through conduits in the floor centuries ago and thus the Koreans can be credited with pioneer development of radiant heating. In Iceland at present nearly a third of the population uses natural thermal water for domestic heating." The Reykjavik system pipes hot spring water at about 94°C throughout the city and has devised insulated double pipes that allow the water to be piped for some 25 km with a drop of only 1°C for every 5 km. The actual cost to the Icelandic consumer is only one-third the cost of heating by imported coal and yet the industry is one of the most profitable in Iceland. The most profitable use of geothermal energy has been its conversion into electricity which can be transmitted economically much greater distances than hot water. The largest installation at the present time is that at Larderello, Italy, where the Count of Larderello began to experiment in the production of electricity from geothermal steam 60 years ago — in 1904. He installed his first steam turbine, with a capacity of only 250 kw, in 1912 as the result of a local quarrel with the power company which furnished the current required in the Larderello chemical industry - an industry that then dated back nearly a century. As experience was gained in drilling deep holes to tap geothermal steam and in converting it to electric power, the capacity of the installation of Larderello gradually increased, but was all destroyed by the Germans during their retreat from Italy in the closing

Jan 1, 1965

By J. E. Burke, C. S. Barrett

THE fine lines shown in Fig 1 are typical of markings that may be detected after polishing and etching deformed specimens of alpha brass and other alloys. Although they have long been the subject of discussion by metallurgists their nature is still uncertain and the names that have been applied to them, such as deformation lines or strain markings, indicate this uncertainty. In this paper which reports the results of a further investigation of their nature, they will be called strain markings. INTRODUCTION Matthewson and Phillips1 in 1916 concluded that strain markings appeared only after deformations that exceeded 20 pct. They objected to the markings being called slip lines believing this term should be reserved for surface markings produced by plastic deformation. In 1921, Vogel2 described similar striations which appeared after polishing and etching the roughly ground surface of numerous alloys. He reported that the markings were crystallographic in nature, and since they resemble Neumann bands in iron, at least superficially, he assumed them to be mechanical twins. In 1928, Matthewson3 reported work by Phillips which indicated that the lines were more readily produced by impact than by slow deformation and that in many cases the twins inside recrystallized grains were parallel to strain markings in the original deformed grains. This was taken as evidence that the markings coalesce into annealing twins, and hence that they themselves are mechanical twins. Many attempts have been made to [ ] demonstrate directly that the markings are mechanical twins. In 1934, Samans4 described the results of X ray studies of two deformed crystals of alpha brass. Evidence was obtained which could be interpreted to indicate that the strain markings are mechanical twins, and this remains the only direct evidence to this effect. Several other attempts to obtain similar evidence by X ray diffraction have failed5,6,7 although in no case was the original method of Samans employed. An

Jan 1, 1948

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By Milton Williams

A comparison is made between the amount of interstitial water found by analysis in cores and that estimated from the resistivity curve of the electric log for the corresponding strata of producing reservoirs. It is shown that while the determined and the estimated water saturations are in good agreement in some cases, this agreement may be due to a fortuitous compensation of errors. Estimates of water saturations made from the electric 1og by use of existing relations should, therefore, be employed with caution. Also presented are data on the variation of salinity of interstitial waters in reservoir sands, and on the effect of variation of salinity and porosity on the validity of estimates of water content made from the electric log. INTRODUCTION Throughout the history of electric logging there have been recurrent cycles of optimism and pessimism as to the value of the electric log in the quantitative estimation of reservoir fluid content. The very early days of electric logging were an optimistic period, in which there was widespread faith in the ability of the resistivity curve to reflect fluid content, and in the ability of the potential curve to indicate textural characteristics. In time the accumulation of exceptions to this idealistic behavior brought about a general disillusionment, and caused the more pessimistic of those dealing with electric logs to believe that the sole importance of the log lay in stratigraphic correlation. Within the last several years optimism as to the quantitative use of the electric log has been revived, primarily as the result of the stimulating work of C. E. Archie' on the estimation of interstitial water in sands from resistivity data. Even though the general trend of thought on the quantitative value of the electric log reflects optimism, it is inevitable that there are some widely divergent opinions of the validity of quantitative estimates based on the electric log. A valid method of estimation of fluid content by means of the electric log and a general knowledge of the textural character of the reservoir rock would be of signal importance, not only in that it would save time and money in securing information on reservoirs now being drilled, but also because it would permit the evaluation of reserves in many fields drilled without adequate core data subsequent to the advent of electric logging. Because of this importance, Humble's Production Research Division, in cooperation with various other company divisions, initiated several years ago series of tests designed to evaluate the reliability of estimates of fluid content made from the electric log. The investigation was limited at the outset to sand reservoirs, since it was felt that the inclusion of limestone reservoirs would entail needless complications. In devising these tests it was immediately apparent that the chief difficulty in evaluating the worth of any method of estimation lay in establishing the true value of fluid content. The results of direct analyses of cores cut with ordinary mud were not sufficient, because of the probability of contamination of the fluids by filtrate from the drilling mud; the results of restored state tests on cores were deemed unsuitable because these results can hardly be said to furnish a primary standard. The method adopted was the direct analysis of cores cut with an oil-base drilling fluid. Such cores, when properly handled, are believed to afford the most precise determination of water content available at the present, and, in addition, lend themselves readily to the determination of various other properties which are pertinent to the estimation of fluid content from the electric log. Since it was desired to compare the fluid contents estimated from the electric log run in ordinary mud with cores cut in the same hole, the use of oil-base fluid necessitated the changing over, after all cores were cut, to a conventional mud. This procedure presented several advantages, one of which was that the use of oil-base fluid permitted

Jan 1, 1950

By C. L. Prokop

A laboratory investigation has been made of the effects of mud hydraulics upon the formation and erosion of mud filter cakes. The tests were conducted to simulate drilling conditions as nearly as possible. The formation of mud filter cake in a drilling well does not proceed at a uniform and unbroken rate. Instead, the rate of cake accumulation depends upon whether or not the mud is being circulated. If the mud column is quiescent, filter cake formation is a smooth function of the filtration characteristics of the system. If the mud is being circulated filter cake formation depends not only upon the filtration characteristics of the mud but also upon the erosive action of the flowing mud column Filter cakes formed during continuous mud circulation were observed to reach an equilibrium thickness after several hours' circulation. Mud circulation was maintained at a constant volumetric rate throughout each experiment. The fluid velocity at equilibrium cake thickness was dependent upon the thickness of the filter cake. Muds having exceptionally high water loss deposited thick filter cakes in spite of very high eroding velocities. The muds having good filtration characteristics deposited thin filter cakes at equilibrium circulating velocities well within tile range of those in a drilling well. It was observed that filter cakes deposited during stagnant filtration were quite difficult to erode by mud circulation. The - rate of crosion computed from the rate of filtrate accumulation after equilibrium cake thickness had been reached was in reasonable agreement with the rate of erosion obtained by direct observation. Continuous mud circulation usually caused the permeability of the filter cake to decrease with time. INTRODUCTION Many of the difficulties encountered during tile drilling of a well have been attributed to the loss of water from the mud and the attendant deposition of solids upon the walls of the hole. Past experience has shown that a reduction of the filtration rate of the drilling fluid eliminates or greatly reduces these difficulties. Definite filtration requirements, however, are hard to establish for a given set of conditions. This is due. in part, to the fact that the usual filtration test performed upon mud doe? not simulate well conditions as closely as desirable. The filtration characteristics of a mud are customarily determined by means of the standard low-pressure API wall-building tester.' In this instrument a filter cake is deposited upon a horizontal bed under a pressure differential of 100 psi. The rnud is quiescent during the filtration period. In actual practice. mud filtration occurs within a well under quite different conditions. One of the major differences is that mud flows upward across the filter bed as the filter cake forms. This undoubtedly produces a change in the filter cake which cannot be reflected in the results of the API test. The laboratory work described in this paper had as its primary objective a better understanding of the influence of mud circulation upon the thickness and ,characteristics of the filter cakes deposited under conditions similar to those existing in a drilling well. ANALYSIS OF PROBLEM Once a permeable formation is penetrated by the bit, filtrate from the mud flows into the formation. 'he mud solids plaster against the walls of the hole, forming a filter cake. If the mud column is stagnant, that is, if it is not being circulated. the filter cake will increase in thickness until the hole is filled. Prior to the time that the hole is filled, the thickness of filter cake existing at any given time will be a function of the filtration characteristics of the mud, the temperature, and the pressure differential. The effects of these variables have been investigated in the past for both flat bed filtration2'3 and for radial filtration.' When the mud is circulated in a hole in which a filter cake i. being deposited. some of the solids that would ordinarily deposit in the filter cake will be carried away by the eroding action of the mud. This will limit. filter cake thickness. Some work has been done to determine the effect of flow upon the filtration rate in a circulating mud system' but little work has been done upon the factors which determine the filter cake thickness existing in a circulating system. On first sight it would appear that the major factors controlling filter cake formation in a circulating system should be: 1. The rate of deposition of solids from the mud. 2. The erosive force that the flowing mud exerts upon the filter cake. 'A. The erodabilitv of the filter cake. 4. Any change in filter cake characteristics attributable to the scouring action of the mud. The rate at which solids are deposited from the mud will be controlled to a large degree by the filtration characteristics of the mud, the pressure differential. the temperature under

Jan 1, 1952

By Wheeler Davey

WHEN metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Langenkugel), and reflection circles of Polanyi,1 Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1929

By Clair Upthegrove, Elbert S. Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are: obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from. 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

By Howard N. Eavenson

The mines of the United States Coal & Coke Co. are located in the Pocahontas coal field, in McDowell County, West Virginia. Twelve plants have been opened and equipped, of which, by reason of the present business depression, only nine are now in operation. These twelve plants serve eighteen mines; some of the plants having several openings, in either the same seam or in different seams, tributary to the same tipple. Only nine of these mines are now being worked at the plants in operation. Construction work was begun in 1902, and coal from the first three plants started was shipped in December of that year. An additional plant was opened in 1903, two in 1904, two in 1905, two in 1907 and the last two in 1908. On Jan. 1, 1915, the plants have been in operation an average period of 8.8 years. The rules of the company, which have been in operation since work was first begun, are similar to those in use by the H. C. Frick Coke Co. at its mines in Pennsylvania, in which " Safety First" was incorporated as early as 1907; and it has always been the policy of both companies to look carefully after the safety of their employees. Although the field is an extension of the old Pocahontas field, the mines, located upon a new branch railroad, are away by themselves, and, as is usual in such cases, the class of labor attracted at first was temporary in character. The rapid development of the mines required the employment of many new men and officials each year; and, while the accident record from 1904 to 1909 was as good as the average of the field, it was felt to be not as good as it could be made, and a determined campaign was inaugurated for preventing accidents of all kinds. Fig. 1 shows the tonnage of coal produced per fatality, both total and for inside accidents only, at our mines; the tonnage per fatality of all West Virginia mines, and of those in the Pocahontas field. The purpose of this paper is not one of congratulation on the results so far accomplished, since the operating officials are not at all satisfied that the maximum is in sight, to say nothing of its having been reached; but to describe the organization and methods that have produced these

Jan 1, 1915

By David R. Mitchell

THIS paper is limited primarily to a description of dry coal-cleaning processes in which air currents are used to effectuate a separation between coal and refuse. Processes depending mainly on differences in the coefficient of friction, resilience and shape are not described unless the use of air is necessary for the proper functioning of the process. The air cleaning of coal is of primary importance to the coal industry of the United States. From figures presented in the 1941 edition Mechannual,1 it is estimated that at least 12 million tons of bituminous coal was cleaned in the United States during 1940 by machines using air as the separating medium. One of the current problems confronting the coal-preparation engineer is the dry cleaning of small sizes and slacks. Progress in machine development for the cleaning of small sizes has been slow in recent years in the United States of America; it has been much more rapid in Britain and on the European continent. This paper does not attempt an exhaustive survey of all these developments, and only machines and processes that have found considerable commercial application are cited. Further, no critical analysis has been made of the theory involved in the separation of coal from refuse by processes using air as the separating medium other than that necessary for an understanding of particular machine designs and applications. HISTORICAL SUMMARY The possibility of using air for the separation of coal from refuse was recognized early by mining men and many attempts were made to develop commercial machines. The ingenuity of the early experimenters is to be marveled at in view of their lack of knowledge of the theoretical principles involved. As in other arts, practice has largely preceded theory. Yet, science and practice play a game of leap frog, now one ahead, then the other; the careful experimenter governs his efforts along practical lines by adapting his experiments to the limits prescribed by scientific laws. By first studying developments and the theory involved, it is not only possible to adapt processes to new uses but also to reduce materially operating cost and to build larger units without costly failures. Although many inventors have applied for patents for separating minerals by the use of air currents, the literature in regard to coal is meager. Berrisford2 describes briefly some of the early attempts to clean coal without the use of water. Several of the examples cited by him are reproduced herein. Fig. I shows a machine used for grinding and sizing, in which rollers running in a pan with a perforated bottom and fan opening on the side crushed the coal, which was then carried by the air currents to a settling chamber. The heaviest particles dropped out first and the light ones farthest away, as shown. In the year 1864, a machine was made that could be used as a sizer or to separate dirt from coal with a sized feed (Fig. 2).

Jan 1, 1942

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1'761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant' used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.' The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*'1' of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967

By T. K. Perkins, O. C. Johnston

Because of the influence of dispersion on miscible-displacement processes, diffusion and dispersion phenomena in parous rocks are of current interest in the oil industry. This paper reviews and summarizes a great deal of pertinent information from the literature. Porous media (both unconsolidated packs and consolidated rocks) can be visualized as a network of flow chambers, having random size and flow conductivity, connected together by openings of smaller size. In such a porous medium, the apparent diffusion coefficient D is less than the molecular diffusion coefficient Do, as measured in the absence of a porous medium. For packs of unconsolidated granular material the ratio D/D, is about 0.6 to 0.7. For all porous rocks, both cemented and unconsolidated, the ratio of diffusion coefficients can also be represented as D/Do = 1/FF where F is the for- mation electrical resistivity' factor and 4 is the porosity. If fluids are flowing through the porous medium, dispersion may be greater than that due to diffusion alone. At moderate flow rates the porous medium will create a slightly asymmetrical mix zone (trailing edge stretched out), with the longitudinal dispersion coefficient approximately proportional to the first power of average fluid velocity (if composition is nearly equalized in pore spaces by diffusion). If the velocity in interstices is large enough, there will be insufficient time for diffusion to equalize concentration within pore spaces. In this region, longitudinal dispersion increases more rapidly than fluid velocity. At low velocities in interstices, transverse dispersion is characterized by a region in which transverse diffusion dominates. If the fluid velocity gets high enough, there will be a transition into a region where there is stream splitting with mass transfer but with insufficient residence time to completely damp-out concentration variations within pore spaces. There are several variables that must be con- trolled to get consistent longitudinal and transverse dispersion results, viz., (1) edge effect in packed tubes, (2) particle size distribution, (3) particle shape, (4) packing or permeability heterogeneities, (5) viscosity ratios, (6) gravity forces, (7) amount of turbulence, and (8) effect of an immobile phase. INTRODUCTION Diffusion and dispersion in porous rocks are of current interest to the oil industry. This interest arises because of the influence of dispersion on miscible-displacement processes. In a recovery process utilizing a zone of miscible fluid, there is the possibility of losing miscibility by dissipating the miscible fluid or by channeling or "fingering" through the miscible zone. Diffusion and dispersion are two of the mechanisms that may lead to mixing and dissipation of the slug. On the other hand, dispersion may tend to damp-out viscous fingers which may be channeling through the miscible slug. 58 Hence, dispersion may be detrimental or beneficial (if it prevents fingering through the miscible zone). Therefore, it is doubly important that we understand these processes. In this paper we review, summarize and interpret a great deal of information from the literature. In particular, we will briefly discuss molecular diffusion in miscible fluids. Then we will discuss what differences to expect for diffusion in a porous rock. If there is movement of the fluid through the rock, then there may be an additional mixing or "dispersion". Furthermore, the dispersion longitudinally (in the direction of gross fluid movement) and transverse to the direction of fluid movement will not be equal. We will discuss both types of dispersion as well as several variables which can affect dispersion (viscosity differences, density differences, turbulence, heterogeneity of media, etc.). This group of variables has sometimes led to difficulty when comparing literature data. DIFFUSION OF MISCIBLE FLUIDS If two miscible fluids are in contact, with an initially sharp interface, they will slowly diffuse into one another. As time passes, the sharp interface between the two fluids will become a diffuse

By John L. Ham, Robert M. Parke

The melting point of molybdenum is 2625° + 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. I, 1944, to Aug. 31, 1945, the project was under the supervision of the National Research Committee, Division One. In peacetime, too, there are needs for molybdenurn, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. First Process for Melting and Casting Molybdenum The maintenance of a temperature greater than 2625°C. in a 'pace large enough to melt several pounds of molybdenum may involve the loss of heat at a Very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum- In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1947

By Frank H. Macpherson

Few people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total Of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,7252 tons in the period 1931 to 1941. It became apparent early in the year '94' that the united States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. AS more than 95 per cent of the known bauxite reserves of the United states was in Arkansas, careful preliminary studies were made in that state by representatives of the united States Bureau of Mines, the United States Geological survey and the War Production Board in the summer of 1941 Reserves in other states also were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite.producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry weight) set for Arkansas by the war Production Board was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place,

Jan 1, 1946

By C. E. Mills

The Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district—the United Verde and the United Verde Extension—lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Woodchute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. T-bis strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the

Jan 1, 1925

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.' Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.' The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt's observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt's earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.' The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.' and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,' or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969

By Norman Carmichael, John Kiddie

The problem of transportation in the Clifton-Morenci district of Arizona has been one of peculiar difficulty and consequently has been an important factor in the cost of mining and treating the ores produced. From the crude beginning made over 50 years ago, many changes have been necessary to keep pace with the increased output of copper. A heavy-duty haulage system has developed on the original 20-in. track gage to meet the existent metal-mine conditions. Topography The transportation difficulties of this district may be readily appreciated from the relief map shown in Fig. 1. The northern half of the district is high mountainous country and there is a general but irregular drop toward the southern part, where the country, although still rugged, is in reality a great sloping plain. This is cut by numerous ravines from which the waters, in the rainy season, discharge into the channel of the San Francisco River. A chasm, 1000 ft. deep, has been eroded through the center of the district by Chase Creek, which is flanked by high irregular mountain masses, notably Copper Mountain, American Mountain, Coronado Mountain, and Markeen Mountain. The latter rises 2300 ft. above the bed of the creek, The San Francisco River has also cut a deep channel, though it is somewhat broader than Chase Creek. Eagle Creek traverses the extreme southwest portion of the area, where it has carved picturesquely through vast volcanic flows. Faulting has left its mark upon the topography of the district by adding to the irregularities caused by erosion. Strong faults occur at the Coro-

Jan 1, 1924