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By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By Charles R. Stewart, William W. Owens

Reservoir performance predictions based on laboratory core test data assume that fluid flow is laminar for the laboratory test. A study has been made to determine the validity of this assumption for laboratory tests on various types of porosity found in producing limestone formation. Data are presented which show that turbulence and slippage can occur during laboratory tests on hetero-geneous-type porosity limestones, thus causing serious errors in measured single-phase permeabilities and two-phase relative permeability characteristics. In single-phase flow tests it is possible to eliminate turbulence and correct for slippage or to eliminate both factors by controlling test conditions. It is not always possible to control test conditions and thereby eliminate turbulence and slippage in two-phase .flow tests. A correction method is presented which can be used to calculate the true two-phase laminar flow relative permeability characteristic even though furbulence and slippage exist. .INTRODUCTION It is customary to make use of Darcy's law and modifications of this law, together with laboratory data on formation core samples to predict the performance of producing reservoirs. Such predictions are based on an assumption that fluid flow is in the laminar or streamline region for the laboratory test. It was the purpose of this inves- tigation to determine the extent to which turbulent flow may occur in laboratory fluid flow tests on hetero-geneous porosity limestones. Considering that turbulent flow conditions might exist in some laboratory fluid flow tests, additional emphasis was placed on the development of a method to correct for turbulence when laminar flow conditions could not be attained. FLUID FLOW CONCEPTS FOR POROUS MEDIA The Influence of Pore Geometry on Fluid Flow One of the more important factors influencing fluid flow in porous media is the geometry of the pore space which includes such characteristics of the pores as size, shape, distribution, roughness, uniformity, etc. In general, oil- and gas-producing formations can be divided into two broad types on the basis of pore geometry. One has been called sandstone-type porosity media, which is characterized by a small range in pore size, uniformity in shape of the pores, smooth pore surfaces and a regular and uniform distribution of pores. The other type has been called heterogeneous porosity media and is usually limited to the dolomites and limestones. This type is characterized by a wide variation in the size, shape, and distribution of the pores and rough, irregular pore surfaces. It is therefore apparent that conditions are much more favorable for turbulent flow* in heterogeneous-type porosity media than in sandstone-type porosity media. Interrelationship Between Turbulence and Gas Slippage In studying the problem of turbulent flow in laboratory tests on porous media, it is necessary to be aware of the interrelationship between slippage and turbulence for gas flow. As a result of slippage or the Klinken-berg effecta, apparent perrneabilities to gas are greater than the true value because there is no stationary layer of gas in contact with the walls of the flow channels. Gas slippage decreases as the mean free path of the gas molecules decreases. Since the mean free path of any gas decreases with increasing density, increases in static pressure result in lower apparent gas permeabilities. However, a reduction in gas permeability can also be due to turbulence. Therefore, in studying only turbulent flow in porous media, it is necessary to hold gas density, and slippage, constant or to reduce slippage to a negligible value by operating at high static pressures. Presentation of Laminar and Turbulent Flow Data A graphical relationship between permeability and a pseudo-Reynolds number, N,, will be used to show the two types of fluid flow, i.e., laminar and turbulent. The usual graphical method for such a description has been the use of friction factor-Reynolds number charts4. On such a logarithmic diagram, the laminar region appears as a straight line having a slope of 45 degrees. As the friction factor decreases and the Reynolds number increases, the turbulent region is reached and appears as a deviation from the 45-degree slope line. However, in petroleum engineering literature resistance of por-

By R. T. DeHoff, F. N. Rhines

The problem of determining the number of particles of a phase distributed randomly in unit volume c an opaque matrix from measurements made on random plane sections is closely investigated. A formalized derivation for the general case is presented. Applications of this formal result are made to specific types of aggregates dispersed in a matrix; circles, particles with flat circular ends, cylinders, and constant shape aggregates of ellipsoids of revolution. Quantitative measurements of the average geometric properties of these aggregates are developed. In 1953 R L. ullman' developed a technique for determining, from measurements made on random plane sections, the number per unit volume, Nv, of particles imbedded in an opaque matrix. Using meas urements previously developed for volume fraction, vV,' and surface area per unit volume, .SV,= he was able to determine average volume, average surface area, and average dimensions of particles, independent of size distribution, for spheres and circular disks,' as well as for uniformly sized cylinders of any axial ratio.4 The technique is mathematically rigorous for the cases studied. Recent studies of this problem have yielded rigorous solutions for the general case of cylinders, permitting evaluation of NV independent of size distribution and with all axial ratios intermixed. Generalization to shapes having flat, circular ends has been deduced. A solution has also been obtained for the ellipsoid of revolution, independent of size distribution, but requiring a constant axial ratio in the generating ellipses. In the following derivations, as in Fullman's work, it is assumed that the problem is purely a combination of geometry and probability theory,that is,eithe the particles to be measured are imbedded randomly in the matrix, or a sufficient number of random plane sections are taken to make the sample representative. A relationship exists between the number of par- ticles of a given size and shape that may be situated in unit volume (Ny) and the number of intersections a random plane can be expected to make with these particles (Na). It is the purpose of the following section to derive this relationship. The probability of Intersecting Convex Bodies. Consider a convex, closed surface, that is, one for which no two surface normals point in the same direction, situated at some arbitrary position and orientation in a cube of material that is one unit long at each edge. It is not necessary to assume that this surface is symmetrical. Let planes be constructed in the cube parallel to the top face and at random distances from it. Those planes which lie between the two planes which are just tangent to the top and bottom of the surface will intersect it. The probability that a plane will intersect the body may be defined as the limit of the fraction of planes that lie between the two tangent planes as the total number of planes constructed becomes infinite. This fraction, in the limit, is equal to the distance between the two tangent planes, DV, divided by the total length over which planes are constructed, which has been taken as unity. If the body is now rotated to a new orientation, applying the same argument, the probability of intersection is again numerically equal to the distance between tangent planes. Let DV ($, 0) be defined as the distance between tangent planes of a convex body as a function of orientation, Fig. 1. The probability, Pr, of intersecting the body with a randomly oriented and randomly positioned plane, is then equal to the average value of DV (0, $) over all possible orientations. It may be easily shown that for a system of spherical coordinates the probability of finding an orientation between Q and Q + de, $ and $ + d$ is (1/4n) sin $ dB d$, so that This relationship may be applied to each body in an aggregate of convex bodies. In particular, if the bodies in an aggregate are classified according to size and shape, and the ithsuch class is considered, Eq. 111 may be applied to this entire class, the probability of intersecting any body in this class being

Jan 1, 1962

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

Following is the personnel of the various society and national committees on which the A I M E is officially represented United Engineering Society Officers of the Board, 1920 JOHN VIPOND DAVIES,, President CALVERT TOWNLEY, 1st Vice-president ALFRED D FLINN,, Secretary WALTER M McFARLAND, 2d Vice-president JOSEPH STRUTHERS, Treasurer Finance Committee House Committee WALTER M McFARLAND Chairman GEORGE H PEGRAM W L SAUNDERS

Jan 1, 1923

By V. T. Stringfield, H. H. Cooper

ONE of the earliest investigations of ground water in Florida was made in 1513 when Ponce de Leon arrived at St. Augustine in search of the Fountain of Youth. The history of the development of the water resources of the State shows that the large artesian reservoir that underlies Florida was discovered in the latter part of the last century. Part of that history is given by L. C. Johnson' who states that the first successful artesian well in Florida was drilled at St. Augustine between 1880 and 1882. After the City of Jacksonville failed to obtain a flow of artesian water at a depth of nearly 400 ft and abandoned the drilling, R. N. Ellis, City Engineer, and L. C. Johnson, using Johnson's knowledge of the geologic structure of the artesian reservoir, estimated correctly that artesian water could be obtained at a depth of about 500 ft. Thus began the development of the large artesian system in the northeastern part of the State. In 1908, the Florida Geological Survey issued its first report on the ground water of central Florida. More recent reports give the results of investigations that have been in progress in cooperation between the Florida Geological Survey and the U. S. Geological Survey since 1930. As a result, the ground-water geology and hydrology of Florida are now so well known that ground-water problems such as confronted early investigators no longer exist. However, new problems arise and new discoveries are made as the demand for more ground water increases with the development of the State. Water-Bearing Formations Descriptions of the geologic formations and a map showing their distribution at the surface are given in a recent report by Cooke.' The geologic formations that yield the ground-water supplies in Florida represent only a small part (about 1000 ft) of the total thickness of the sedimentary rocks (more than 15,000 ft) that underlie Florida. The water-bearing rocks that yield fresh water include more than two dozen formations that range in age from Eocene to recent. The Eocene formations, which consist chiefly of limestone, are the oldest and the deepest of the formations in Florida that yield fresh water to wells. In 1944, on the basis of a study of the foraminifera, the Applins -ivided the limestone of Eocene age into six formations, which are as follows, from top to bottom: Age or group Formation Jackson Ocala limestone icAvon Park limestone Claiborne -j Tallahassee limestone aLake City limestone Wilcox Salt Mountain limestone xOldsmar limestone The Ocala limestone and the underlying formations of Claiborne age, along with some of the overlying limestone of Oligocene and Miocene age, constitute the principal source of water in Florida and southeastern Georgia and generally may be regarded as forming one artesian aquifer or water-bearing unit. This aquifer is referred to in this paper as the Floridan aquifer, a name proposed by Parker.' In part of Seminole County alone more than 1000 flowing wells yield water from the Floridan aquifer. A yield of 6500 gpm, or about 9.5 million gal per day, by natural flow from a well penetrating the aquifer at Jacksonville, Florida, was observed in 1942. A yield of about 7000 gpm by natural flow was reported for a well 1390 ft deep at St. Augustine in 1887. The largest yield reported from a pumped well penetrating the aquifer is 7500 gpm, or about 10.5 million gal per day. The aquifer is also the source of some of the large springs, such as Silver Springs, whose discharge, according to measurements made by the U. S. Geological Survey, has ranged from 526 to 1350 sec-ft, or from 340 to 872 million gal per day. The top of the Ocala limestone, as represented by contours in Fig. 1, indicates in a general way the geologic structure of the formations that comprise the Floridan aquifer. The Ocala is at or near the surface in the areas represented by shading in the northwestern part of the peninsula and also in an area in western Florida adjacent to Alabama and

Jan 1, 1952

By E. Wainer, K. D. Burnham

A wet beneficiation technique for producing wollas-tonite from its ore in high yield and purity has been evaluated in a pilot plant operation at the rate of 75 tons per month. Finely crushed, unsized wollastonite ore mixed with water is passed through a high in tensity oscillating wet magnetic separator of unique design and in a single pass over 90% of the wolla-stonite exhibiting a crystal purity of 99.8% is obtained irrespective of size of feed fraction. Thereafter, the material is processed by closed cycle standard wet milling and classification techniques to yield a 1µ size product, though any mesh size up to and including 50 mesh may be obtained, if desired. Costs appear to be significantly lower than those available from dry processed techniques. Wollas tonite made by this unusual wet process appears to have potential utility in the following fields: ceramics, paints, plastics, paper, organic finishes, reinforcement of portland cement items, controlled porosity refractory ceramic foams, cinder and concrete block paint, and the like. The 1µ and certain chemically processed varieties of wollastonite may have unusual utility in the paper industry both as a filler and as a coating material and in the organic finish industry. Extensive deposits of wollastonite ore equivalent to an average tenor of 50% to 60% of this latter mineral in easily separable form exists in and around Essex County in northern New York State in reserves of the order of several tens of millions of tons. While important portions of these deposits are susceptible to open pit mining techniques, one operation near Wills-boro, N.Y., involves tunnel mining and dry milling and beneficiation techniques. This mill and tunnel mine is presently being operated by The Cabot Corp. and a variety of particle sizes are now sold into markets in the ceramic, paint, plastic finish, floor tile and in similar fields in substantial tonnages on a repetitive basis. Serious investigation and study over the past several years has indicated that, outside of the obvious economies of open pit techniques for mining purposes, wet beneficiation and milling procedures applied to the ore not only represent a potential for greater economies in the production of a superfine finished product but yields products of improved properties exhibiting increased market potential which may not be available from the dry ground product. The Lewis and Deerhead deposits, controlled by the Adirondack Development Corp., appear to be identical to the Wilisboro deposit. Utilizing ore taken from the Lewis and Deerhead deposits, a pilot plant process for the wet beneficiation, milling and classifying of wollastonite ore has been operated for several months. After scalping a marketable garnet product from a minus 16 mesh dry crushed feed on a high intensity roll magnet the balance of the material is then roll crushed in a closed cycle until it will pass a 50 mesh screen. The product constitutes the feed of the wet magnetic separator. The heart of the new beneficiation process is a cyclically operated wet magnetic separator which exhibits the unique feature that unsized feed is easily handled. Product yields of higher purity are equal to that obtained with dry magnetic separations which use closely sized dry ore and multiple passes, but only produce wollastonite of about 98% mineral purity as determined by sink float techniques. It was anticipated that the wet processing through the grinding, milling and classification stage would yield a low cost 1µ ground product which should make available greatly increased applications for the mineral beyond those presently enjoyed. The improved purity was also expected to provide coarser sizes which might be utilized as a raw material for chemical modification which again would expand the uses of wollastonite. The evidence thus far collected appears to indicate that this premise may be expected to be fulfilled. There are on the surface of wollastonite particle sites at which cheinical reactions may occur1. It is believed that wet ground material provides a better base which will allow wollastonite a deeper entree into the field of chemical raw materials. Wet ground at 20µ and finer permits with certainty a number of chemical reactions, some of which are mentioned later in this article. While well crystallized wollastonite makes up the majority of the ore, the balance consists mainly of very weakly magnetic diopside of the hedenbergite-

Jan 1, 1965

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,'. ' Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957

Executive SIDNEY J. JENNINGS, Chairman. GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 6, 1918

By J. D. Testerman

A statistical technique to identify and describe naturally occurring zones in a reservoir and to correlate these zones from well to well is described. The technique is particularly useful in describing a reservoir where cross flow between adjacent strata is important in determining reservoir behavior. Although it has been used primarily for permeability zonation, the technique is general and can be used to correlate any reservoir property or related data, such as the information contained in well logs. INTRODUCTION One of the first problems encountered by the reservoir engineer in predicting or interpreting fluid displacement behavior during secondary recovery processes is that of organizing and using the large amount of data available from core analysis. Permeabilities pose particular problems in organization because they usually vary by more than an order of magnitude between different strata. Due to the sheer volume, it is almost always necessary to group data and to use an average value to represent a number of measurements. Perhaps the most common method now used to group permeability data is the capacity-fraction technique, which ranks permeabilities in order of magnitude, regardless of the physical location of the permeabilities within the reservoir. The cumulative per cent capacity is plotted against cumulative per cent thickness. This plot is divided into an arbitrary number of zones, generally of equal thickness. Five zones (or averaged groups of data) usually are obtained, each of which is treated as homogeneous in subsequent calculations. The division so obtained has no physical meaning; strata in the same zone, calculation-wise, are usually not adjacent in the reservoir. Reservoir engineering techniques being developed will handle crossflow that occurs between adjacent communicating reservoir strata because of imbibition and gravity segregation. Since crossflow occurs between physically adjacent layers within the reservoir, a new zonation technique recognizing the actual location of strata within the reservoir is necessary. Similarly, the recognition of natural zones is important for predictions of oil recovery by processes involving diffusion. One such process is miscible displacement, where predictions of lateral diffusion within the reservoir must recognize the actual location of the invaded zones in relation to the rest of the formation. Natural zones must also be adequately recognized to account for heat transfer within the reservoir during thermal exploitation. Because of the complexity of the problem, statistics appear to offer the only practical hope of dividing a reservoir into physically-meaningful natural zones. This paper presents a statistical technique for identifying these natural zones and for ascertaining which ones are likely to be continuous between adjacent wells. The zones defined have minimum variation of permeability internally and a maximum variation between zones. The technique is general and can thus be applied to reservoir properties other than permeability. The method will guide the reservoir engineer in estimating which zones are likely to be continuous between wells. However, a statistical correlation based on permeabilities in two different wells is no guarantee that the zones so defined are, in fact, continuous. Rather, the assumption of continuity must be consistent with geological data concerning the depositional environment, as well as justified on the basis of engineering judgment in combination with statistics, just as judgment is required with conventional zonation methods. CALCULATION PROCEDURE The reservoir zonation technique is a two-step operation. The steps are individually described, and a sample calculation is presented in the Appendix. ZONATION OF INDIVIDUAL WELLS First, the set of permeability data at a single well is zone, into Zones. These zones are selected so that variation is minimized within the zones and maximized between the zones. The equations4,6 used to zone the data are where B = the variance between zones, , = the number of zones, i = the summation index for the number of zones, j = the Sumation index for the number of data within the zone, mi = the number of data in the ith zone, k,. = the mean of the permeability data in the ith zone, k . = the over-all mean of the data in the well, W = the pooled variance within zones, N = the total number of

By Claude H. P. Lupis, John F. Elliott

IN the recent past, extensive use has been made of the interaction coefficient in treating the thermody-namic behavior of components in solutions at dilute concentrations. The development of this concept by wagner1 and chipman2,3 is sufficiently well-known so that its elucidation here is not necessary. The present discussion is focused on the relationship between E and e. The usual forms of the coefficients are:

Jan 1, 1965

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.' Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.' Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Walter Kauenhowen

The production of crude oil in Germany during 1934 totaled about 2,200,408 bbl., a 33 per cent increase over the 1,670,109 bbl. produced in 1933. This is an extension of a yearly increase which has continued uninterruptedly since 1928. Producing Fields The 1934 increase in production is due chiefly to developments in the north district of the Nienhagen field, where the production in 1934

Jan 1, 1935

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 11, 1918

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C.' STONE2 J. H. JANEWAY4 BRADLEY, STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 7, 1918

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT-M. RAYMOND Membership LEWIS W. FRANCIS KARL EILERS, Chairman J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY.1 Chairman. ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 2, 1919

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958