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By G. A. Vissac

The only fine coal washer with proved automatic controls, the feldspar jig is capable of good efficiencies even at low separating gravities, handles a variety of products, and treats 150 tph and over. IN continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from % in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals. Theory of the Feldspar Jig To understand fully the operation of the feldspar jig and to appreciate its potential value, it is necessary to measure and analyze the motion of small particles of various specific gravities, falling in various media, under various conditions. As no practical formulas were available for that purpose, the writer has developed new theories and established new sets of formulas, which cannot be demonstrated here. They are applicable to all minerals and to many problems of coal or mineral concentration. These formulas do not pretend to absolute accuracy, but results, tested by comparison with experimentally recorded data, are sufficient for practical purposes, as they give definite indications of trends, relative values, and order of magnitude of the many factors involved. For pulsating motions no earlier formulas are available. In the case of continuous currents or motions, such formulas as Rittinger's, Allen's, or Stokes', over a hundred years old, apply only to special shapes and sizes of particles, involve factors and coefficients difficult to measure or appreciate, and deal only with free motions. They are of little use in solving practical problems. Units used with the formulas presented here are in the CGS system. Lateral friction and suction have been taken into account according- to methods currently used in aerodynamics, and only hindered motion is dealt with. As the feldspar jig is primarily intended to create a fluid bed condition, the mixture of fluids and solids obtained is homogeneous, and the apparent specific gravity of the separating medium is calculated accordingly. For instance, if 20 pct of the volume is coal and shale, with an average of 1.60 sp gr, in a liquid of 1.10 sp gr, the actual specific gravity of the separating fluid is 0.80 x 1.1 + 0.20 X 1.6 = 1.20. The fundamental equations are as follows: The general motion of a particle falling in a medium of specific gravity equal to u, hindered motion. is dv/dt = g/Ls [ L (s-u) - u/g v2 [1] g = 981 cm per sec, acceleration of gravity, and L = thickness of the particle of specific gravity (s) and velocity (v). The initial acceleration dv/dt = g (1-u/s ) [2] is a function of the specific gravity of the particle, only for a given medium, and independent of its dimensions—an ideal separating condition. The terminal velocity Vt = gxL- (s-u)/u, [3] for a given value of u, is a function of s and L. Two particles, L, s, and L2 s2, are said to be equivalent if they have the same terminal velocity, and accordingly L1/L2=s2-u/s1-u. [4] Two such particles cannot be separated by continuous currents, in any concentrating device. Because the initial accelerated motion, which provides for efficient separation, is followed by a constant velocity, which has a limiting effect, it is essen-

Jan 1, 1956

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By Wolfgang O. Gluschke

INTRODUCTION Virtually all countries have general legislation covering most aspects of mining and mineral processing, including investment and tax laws, safety and health regulation, and specific rules applying to exploration reporting procedures. Yet most developing countries negotiate individual agreements with foreign investors for major mineral projects, in particular when all or part of the expected output is exported. Such agreements are known under several different names, as for example concession agreement; technical assistance agreement or service contract; management agreement; production sharing contract; joint venture; or contract of work. The objectives and conditions governing such contracts are as diverse as these titles are. While a mining project is only one among a large mumber of similar undertakings in industrial countries, in most developing countries such projects usually have a dominating position within the country's economy. The general legislation is often inadequate and insufficiently detailed to cover all aspects of large projects with extensive foreign inputs and international markets. Therefore, the need for specific arrangements. Specific arrangements may also become necessary due to the complexity of markets for mineral products, the large number of participants - equity partners, suppliers, financial institutions, buyers, etc. - or economic and political conditions in the host country and fiscal regulations in the home country of the investors. Most agreements are concluded between governments, or government agencies, in developing countries and private industry headquartered in developed market economies - Canada and the United States of America in North America, Western European countries, Japan, South Africa and Australia - or, in some instances, with state-owned firms in these countries. There are fewer agreements between developing countries and the centrally planned economy countries - Eastern Europe and the USSR - which cannot be considered here because of absence of adequate information. Agreements can be concluded at any of the different stages from exploration through closing of a mine. While most contracts are negotiated at the time when a potentially viable ore body has been delineated and investigated sufficiently to anticipate a realistic time for commencement of production, other agreements start with "grass-roots" exploration, during operation of a mine, smelter or refinery or, exceptionally, after a temporary shutdown. While several major provisions are included in all types of agreements, others are covered in much more detail (or not at all) in some contracts reflecting the specific work programme of each project. While it is realized that subdivision and classification of complex contractual relations is necessarily arbitrary to a certain extent, such grouping is useful in practical terms, especially for the non-specialist. The following discussion, therefore, will start with a description of the major forms of contractual relation - concession, investment contract, joint venture, management agreement, service and production sharing contracts. Major issues covered in all, or almost all, agreements will then be dealt with. These include stages of development, corporate structure and control, fiscal arrangements, infrastructure development and environmental law, and dispute settlement and renegotiation. FORMS OF CONTRACT RELATIONS There has been marked change in the type of agreement entered into during the 1960s (and before) and the early 1970s and the period thereafter. While straight "concessions" - granting of exclusive rights to foreign investors over a certain deposit or areas with little restriction or well-defined obligations - were the rule during the first half of this century, more complex agreements have evolved since. Some of these cover every conceivable aspect, foreseen or only possible, and define rights and obligations of all partners to the last detail. Over the years, agreements have without doubt become more beneficial for the developing host countries, in part as a result of well-publicized nationalizations, as for example in Chile, and in part due to changed attitudes in all countries

Jan 1, 1985

By G. H. Enzian

THE effects of phosphorus and nitrogen on the properties and behavior of low carbon steels are important considerations to both the manufacturer and the user of such material. For one thing, these two elements are the principal points of distinction between the chemical compositions of Bessemer and open-hearth grades. Further, open-hearth steels themselves may vary considerably in nitrogen content depending on the raw materials and ..practice used. In addition, appreciable amounts of rephosphorized open-hearth steels are being used at the present time in some low alloy, high strength grades and in certain other cases. For these and other reasons, it was felt desirable to obtain more complete knowledge of the effects of simultaneous small variations in phosphorus and nitrogen content on such properties of low carbon steel as tensile strength, impact toughness, sensitivity to cold work, and strain aging. A long range investigational program designed to furnish such information, was carried out, and the present paper summarizes some of the data currently obtained. General Discussion The strengthening effect of relatively small amounts of phosphorus in steel has been recognized, and to some extent utilized, for many years. A number of investigators have pointed out, from time to time, that under proper conditions of control, phosphorus can be a useful alloying element in low carbon steels.1-3 Nevertheless, in spite of the volume of data on the subject, the use of phosphorus for this purpose has always been handicapped by widespread feeling that its presence makes the steel brittle, difficult to cold work, and unreliable at low temperatures. This belief on the part of some steel users is not entirely justified in many cases, and often stems from early experience with acid Bessemer steels which have appreciably higher phosphorus (and nitrogen) contents than basic open-hearth grades. Nitrogen in steel, and its effect on properties, has also received considerable attention in the literature.4 In 1906, Braune5 ascribed the brittleness of Bessemer rails to the nitrogen content, and proposed a schedule of nitrogen limits for steels for various uses. This was one of the first papers to recommend directly the use of nitrogen content as a quality control measure, but it did not meet with much favor or support; as a matter of fact, the Jernkon-toret was rather sharply criticized for publishing the paper. In the intervening years a number of papers have been published on the subject of nitrogen in steel. As a result, it is now generally recognized that nitrogen can have an important effect on the properties and behavior of steel and that the presence of this element should be considered in any systematic study of factors affecting steel quality. In 1932, Graham6 introduced the concept that the quality of various steels could conveniently be evaluated and compared in terms of "sensitivity", which was defined as "the characteristic reaction rate of a piece of steel toward brittleness or hardness." This concept formed the basis for a broad research program into factors causing variations in the quality of commercial steels. At an early stage of this work, it became apparent that the observed effect of either phosphorus or nitrogen on the sensitivity of steel depended, in no small measure, on how much of the other of these two elements was also present. Indeed, the combined effect of phosphorus and nitrogen in steel may often be more important than the specific effect of either. With a few exceptions, it is not possible to predict accurately the effect on steel properties of a change in the amount of either phosphorus or nitrogen in the steel without also specifying the approximate amount of the other element. It seems desirable, at this point, to discuss briefly the distinction between strain-sensitivity and strain aging as used in this paper. In the early stages of its development, the work-brittleness test7 (which will be described in more detail later) was used

Jan 1, 1951

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By F. W. Jessen, N. Mungan

The plastic flow characteristics of clay water suspensions were first recognized by Binghaml in 1916 and further studied by Ambrose and Loomis' in 1931-1932. Many physical and chemical properties of clay suspensions are deeply influenced by particle size distribution as well as by the exchange cation. Separation of a number of fractions is particularly helpful in making a detailed study of a suspension. A limited amount of work has been conducted on the effects of particle size on specific properties of mud drilling fluids. A knowledge of particle size distribution is essential for a better understanding of fundamental properties of clay suspensions, particularly viscosity and gel strength. The purpose of this investigation was to study the effect of particle size on the viscosity and gel properties of clay suspensions and to determine any changes in mineral composition accompanying variation in size. EXPERIMENTAL PROCEDURE Numerous methods may be used to fractionate a poly-dispersed clay suspension into nearly mono-dispersed systems. Particles larger than 44 micron (325-mesh) may be obtained by wet screening. For sizes from 44 to 1 micron, the fractionation may be accomplished by sedimentation, elutriation plus microscopy,' or turbidimetry.6 When dealing with systems which contain a major portion of particles below l-mi-cron size, slit ultramicroscopy,7 centrifuge methods of Svedberg,5 eams,9 and McBain,l0 and X-ray methods" may be employed. The Sharples super centrifuge has been proved suitable for the economical separation of suspended particles of submicron range.12,13,14 Three-hundred and forty-five gal of 1 per cent by weight Aquagel suspension was mixed in a high-speed 5-gallon mud mixer and the suspension was allowed to stand in 5-gal glass bottles for 30 days to assure full hydration. All particles larger than 44 microns were removed by wet screening. Five fractions in the range of 44 to 1 micron were obtained by sedimentation. The Sharples super centrifuge method described by Hauser and Reed.13 Norton and Speil,14 Ha user and Lynn,15 and Hauser and Schachman,10 as employed to yield five fractions of submicron size. A super centrifuge operation chart prepared by Fancher, Oliphant, and Houssierre12 was used to determine operating conditions for the desired particle ranges. The clay suspension, after removal of all material above 1-micron size, was centrifuged. During rotation of the bowl, the particles were deposited on a thin plastic liner which fit closely inside the bowl. After passing 5 gal of suspension through the centrifuge, the liner was removed and the particles on the liner were scraped off, remixed and recentrifuged. This was repeated five times. Thus, Fractions H, I, K, and L were obtained. The finest fraction, M, remained in an approximately 0.4 per cent suspension. Water was evaporated under reduced pressure from this suspension to yield the finest particles. Results of the fractionation are included in Table 1. In order to achieve proper orientation and humidity conditions for X-ray diffraction analysis, the following procedure was employed. The dilute suspensions were placed on glass slides and allowed to dry at room temperature. This was repeated several times. Previous to measurement each sample first was placed in a water desiccator for half an hour and then allowed to stand for 15 minutes at room temperature. thus yielding an equilibrium condition of about 52 per cent relative humidity. The relative humidity of the room in which the X-ray diffraction was carried out was maintained at approximately 50 per cent so that there was no change in the spacings during the X-ray examination. Samples

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By M. R. J. Wyllie, Walter D. Rose

The use of electrical well logs for the quantitative determination of such reservoir parameters as connate water saturation, formation permeability and connate water salinity has recently been attracting the attention of a number of workers1,2,3,4,5. While the theory of the determination of connate water salinity from the self potential S.P. log has received rather detailed treatment, relatively little attention has been paid to the theoretical aspects involved in the quantitative interpretation of resistivity data. It is clear that if electrical well logs can be used for the quantitative evaluation of physical characteristics of reservoir rock, they will provide a valuable tool to supplement cheaply information obtained by more laborious core analysis. In certain cases it is conceivable that the coring program could be considerably curtailed if the electric log could be relied upon to give reasonably accurate quantitative information. It is our object in this paper to examine the theoretical basis of quantitative log interpretation as expressed in such well-established logging concepts as formation factor and cementation factor. It is also our object to investigate the physical aspects of the rela- tionship which is presumed to exist between resistivity index and brine saturation in reservoir rock. In particular, we will endeavor to draw attention to the fact that it is possible to express these logging concepts in terms of capillary pressure-saturation relationships, permeability and tortuosity, parameters which we will consider in this paper to be fundamentally indicative of rock texture. The probability of being able to obtain from log recordings alone the data theoretically essential to permit quantitative log interpretatiou will be examined, and consideration will also be given to the problem of formulating simple semi-empirical relationships for use in the field. THEORETICAL CONSIDERATIONS The concept of formation resistivity factor, or as it is now commonly called, formation factor, appears to have been introduced by G. E. Archie",". Formation resistivity factor as defined by Archie is the resistivity of a rock 100 per cent brine-saturated divided by the resistivity of the brine. This relationship had previously been used by physical chemists and the concept is, for example, implicit in an early treatment by Fricke7 of the conductivity of aqueous slurries. Archie was able to establish the fact that although the relationship between formation factor and porosity did not change too greatly for different rock textures, the relationship between formation factor and permeability was markedly dependent on rock texture. The relationship found by Archie between formation factor and porosity was expanded by H. Guyod8. Archie had suggested that the formation factor, F, could be expressed in terms of the porosity, F, as follows: F =F-m .... (11 where, F = effective porosity fraction of the sand, and, m = an exponent greater than about 1.3. Guyod introduced the term cementation factor for the exponent, m, since it may be qualitatively shown that formation factor for any given porosity tends to increase as the sand becomes more cemented. It would appear that the concept of m as an exponent representing the cementation in a sand is strictly only of qualitative value, since the quantitative estimation of m by means other than the determination of F and F has not been possible. Guyod suggests that m can be estimated from a visual examination of a sample of rock, but this method appears to be both arbitrary and unreliable. It can be said, however, that in intergranular reservoirs of practical interest, the range of m is from about 1.4 to 3.0. A possible explanation for the fact that m is found to lie between these limits will be offered below. The determination of formation factor is an essential preliminary to the

Jan 1, 1950

By R. J. Wagner, Jim Douglas Jr., P. M. Blair

The calculation of the behavior of an oil reservoir during a water flood has long been an important problem to reservoir engineers. Buckley and Leverett derived the differential equation which describes the displacement of oil from a linear porous medium by an immiscible fluid, but this equation could not be solved by the methods of classic mathematics. Consequently, in order to integrate the equation over the length of the reservoir, they neglected the effects of capillary pressure. In the present paper, a numerical method has been developed for determining the behavior of a linear wafer flood with the inclusion of capillary pressure. The differential equation which was derived for the case of incompressible fluids is second order and non-linear. This differential equation was approximated by an implicit form of difference equation which is second order correct in both time and distance. An electronic digital computer was used to perform the numerical solution of the difference equation. INTRODUCTION The problem of calculating the flow and distribution of fluids in an oil reservoir subjected to a water flood has long challenged the reservoir engineer. The ability to solve this problem would provide a valuable tool for the design and study of field waterflooding programs. One of the first contributions in this field was made by Buckley and Leverett,'.' who developed a method of calculating waterflood performance in a linear reservoir. Their technique was limited by the practical necessity of excluding quantitative consideration of capillary pressure. It is the purpose of this paper to describe a method for calculating the behavior of a linear water flood with capillary pressure considered. This method, although limited to the linear case, should serve as a step toward the solution of the two- or three-dimensional waterflooding problem which would better describe actual reservoirs. The treatment of the problem has assumed that the reservoir is linear and homogeneous, that both oil and water -are incompressible, and that gravitational forces may be neglected, and that water is injected into one end of the reservoir and oil and water are produced from the other. Though these assumptions may not be directly applied to natural reservoirs, they are closely approached in many laboratory core tests. The physical problem has been represented mathematically by means of a differential equation and suitable boundary conditions. The inclusion of capillary pressure effects causes the differential equation to be second order and non-linear, and it is not amenable to solution in terms of known functions. Nevertheless, the problem may be solved by numerical methods. The authors have successfully calculated several cases from the start of water injection through to depletion of the hypothetical reservoir using realistic capillary pressure and relative permeability characteristics that were chosen so as to put the method to a test. DIFFERENTIAL EQUATION In two- or three-dimensional problems involving the two-phase flow of incompressible fluids through a porous medium, the equations describing the flow can be combined until only two dependent variables remain, the pressure in one phase, and the saturation of one phase. These variables appear in two simultaneous partial differential equations which are derived on the basis of the conservation of mass and Darcy's law as applied to two-phase flow. For a linear reservoir, this system of differential equations can be reduced to a single, nonlinear, second order, parabolic differential equation for one dependent variable, the saturation of one phase. For incompressible water and oil, it can be shown that the conservation of mass for the two phases requires that Where q, and q, are the water end oil flow rates per unit cross-section, s, and so their saturations, +, the porosity, and [ and T, dimensional space and time variables. Darcy's law, as extended to two-phase flow including the effect of capillary pressure,' is as follows:

By L. A. Rapoport, W. J. Leas, C. W. Carpenter

A program of scaled flow model experiments has been undertaken to study the performance of five-spot water floods. The modeling procedures are discussed and the construction and operation of the flow models are described. The tests were specifically designed to investigate the effects of injection rate and of oil-to-water viscosity ratio on oil recovery. The areal sweep of five-spot water floods was also studied, and direct comparisons between five-spot and linear flooding behavior have been established to permir better utilizatfon of core analysis results for purposes of field waterflood evaluations. INTRODUCTION For a long time reservoir engineering procedures have been confined to the consideration of idealized, one-dimensional or linear systems.11* However, direct application of the linear waterflood mechanism to the evaluation of actual field performance is justifiable only for the purposes of rough approximation. To obtain a realistic analysis of field behavior, it is necessary to account for reservoir geometry and well distribution, and to take into consideration the configuration of the flow of fluids between injection and producing wells. In the past it has been attempted to account for the complex nature of the fluid movement in the reservoir by associating each well pattern with a certain "sweep-efficiency constant", e.g., a sweep efficiency of 72 per cent for the conventional five-spot pattern.' More recently, methods of waterflood evaluation have been improved by the introduction of variable sweep-efficiency factors, defining the areal coverage as a function of cumulative water injection and viscosity or "mobility" ' ratio.""' These variable sweep-efficiency factors, derived from miscible fluid displacement experiments, require the assumption of piston-like displacement of oil by water. This implies that only one fluid, either oil or water, is moving at any one point of the reservoir ht any moment. Such an assumption, however, is incompatible with the bulk of the experimental evidence and also theoretical considerations which indicate that usually in the area invaded by water, both oil and water are flowing in varying proportions, in accordance with the relative permeability characteristics of the porous medium. Another recent approach toward the evaluation of five-spot flooding behavior involves correlations of the areal sweep efficiency (observed in immiscible fluid experiments) with a "mobility ratio," based on the consideration of the "average" relative permeability to the displacing fluid. Combination of these correlations with a modification of the Buckley-Leverett frontal-drive equation leads to a computational procedure for predicting the recovery performance of areal water floods. While of considerable interest, this approach has no complete theoretical justification and, therefore, does not entirely clarify the features of five-spot water floods. Rigorous, theoretical treatment of waterflood behavior in two- or three-dimensional systems as encountered in the reservoir, including proper consideration of relative permeability and capillary-pressure functions, is as yet beyond the scope of analytical or computational methods. The, behavior of such water floods can, however, be studied by means of scaled flow model ekperiments, which is the approach followed in these investigations. The flow model experiments described in this paper simulate a uniform, horizontal formation of constant thickness with fully penetrating wells. The system under consideration is entirely liquid saturated and not influenced by compressibility effects, which is representative of the situation achieved after gas fill-up under practical conditions. Gravity segregation effects are assumed to be negligible, which implies a relatively thin reservoir formation and/or low vertical permeability. THEORETICAL CONSIDERATIONS For a flow system of uniform thickness with no appreciable effects of gravity segregation, the analysis of water-oil displacement can be confined to a two-dimensional treatment based on the consideration of a "slice" of unit thickness. Referring to previously established derivations," the displacement of oil by water in such a system can be described by the following, dimen-sionless equations:

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By E. C. Tveter, L. A. Roe

The authors present a general outline of the theory and development of heavy-liquid application to mineral processing. Patent literature and processes are reviewed with special emphasis on liquid recovery systems which have been employed or proposed. Advantages and disadvantages of the process are discussed together with the recent developments which have revived interest in this old concentration method. The most important single factor in this resurgence of interest is concluded to be the narrowing gulf between chemical engineering and mineral dressing which has opened the field for new concepts of mineral plant design. A partial summary of patents on heavy liquid separations is included. In spite of the fact that heavy-liquid separation with organic liquids has been used in the laboratory for over 50 years, this process has never graduated to large scale commercial use for any extended period. However, a variation of this process, the sink-float or heavy-media separation process has found wide acceptance and is used to separate minerals from diamonds to gravel. Materials used to increase the specific gravity of the pulps used as heavy media include sand, clay, barite, magnetite, galena, hematite, atomized lead and ferrosilicon. Because of the greater ease of recovery, the magnetic materials, magnetite and ferrosilicon, are the preferred media today. In the U. S. alone, heavy-media iron ore plants with a capacity of over 10 million tons of concentrate per year are in existence. Heavy-media separation involving use of solid, inorganic particles suspended in water rapidly found a wide range of commercial use with the introduction of magnetic media. The minerals engineer is experienced in working with suspensions and quickly learned to develop and control such media at a cost compatible to the type of separation desired. The natural superiority of a heavy liquid with uniform chemical and physical properties has never been questioned since its first use in laboratory mineral separatory procedures. It offers the only method for gravity separation of fine particles of relatively close specific gravity. The most important early attempt to make heavy liquid separations commercial were made by the DuPont Co. which began experimental work on Virginia limonite in 1904. The appended "Partial Summary of Patents" compiled by W.L. O'Connell of The Dow Chemical Co. demonstrates the quantity and sequence of this work. Both inorganic and organic parting liquids were investigated and numerous patents were issued on the use and recovery of these liquids. The work culminated in the heavy liquid plant of the Weston Coal Co. at Shenandoah, Pa. Chemical engineering design of this plant was the responsibility of Francis I. and Hubert I. DuPont. Heavy-liquid separation of coal almost achieved commercial status at this plant which actually processed over 20,000 tons of coal. The liquids used were tetrabromethane, pentachloroethane and trichlo-roethylene, with liquid losses ranging from 8.9 to 12.4 oz per ton of cleaned coal. The reasons for failure of this plant are not clear but probably involved toxicity problems as well as other problems in chemical engineering. Excellent economics were reported. A more recent pilot plant was built in 1954-55 by Norris Goodwin for the Inerto Co. to treat hectorite clay. This plant employed carbon tetrachloride in jigs with liquid recovery by evaporation. Although good separation was achieved, incomplete removal of the CCl, from the clay prevented commercial operation. The only present operations known to the authors employing heavy liquids for gravity separations are limited to the use of calcium chloride in certain coal washers and bromochloromethane in a small batch operation (one ton solids per day) for the separation of beryllium metal particles from slag materials. This is not strictly a minerals beneficiation problem but it has demonstrated the feasibility of such separations. PROBLEMS Critics of early attempts to commercialize heavy-liquid separation of minerals summarize the draw-

Jan 1, 1963

By W. S. Sanner

Experiments were conducted to determine the quantity and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. A low, a medium, and a high-volatile anthracite were studied. Specific gravity separation followed by grinding, screening, and refloating at lighter specific gravities yielded small quantities of material purified to 1.0% ash, as follows: from low-volatile anthracite, 0.7%; from medium-volatile coal, 1.0%; and from high-volatile coal, 2.3%. The reduction in ash had no appreciable effect on the volatile matter or sulfur content of the coal. The limited quantities of material containing 1.0% or less ash obtainable indicate that if ultraclean coal is desired, a practical approach should include the processing units as an integral part of a convc.ntiona1 dense-media washing plant. Anthracite preparation practices during much of the industry's history were geared to maximum recovery of the larger sizes, pea through egg, which were used in hand-fired, domestic furnaces. Those sizes were cleaned to meet trade requirements, and the smaller sizes were usually higher in ash content. The impression, thus, was that ash content of anthracite always increased as the sizes got smaller. It was presumed that it was impossible to wash the finer sizes to extremely low ash contents. Following World War 11, the classical domestic market began to decline and the finer sizes assumed an increasingly large share of the market. For example, in 1949l 61% of the production was still pea and larger. Fig. l2 shows that -by 1955 these sizes accounted for only 50%, and in 1965, they were only 39% of the total anthracite produced. With the reduction in the market, increased quality was demanded, especially in export markets, and an increasing number of dense-media magnetite washers were installed in new and existing cleaning plants. In 1965, the coarse coal prepared at 59 breakers in the anthracite fields was sampled by the U.S. Bureau of Mines (USBM); approximately 50% of these plants were equipped with dense-media magnetite washers.3 Since 1950, more attention has been focused on the use of finer sizes for numerous industrial uses, including iron-ore sintering, pelletizing, foundry coke-making, cement manufacture, production of calcium carbide, and of carbon electrodes, etc. Most industrial uses require relatively clean anthracite, such as 10 to 11% ash for sintering and foundry coke, 7% for aluminum melting-pot cathode carbon, and 5% for carbide production. Hence, cleaning methods have been improved to the extent that dense-media washers, hydraulic cyclones, and flotation cells have been introduced as fine-coal-cleaning devices. It is now possible to wash the buckwheat, rice, and barley sizes (9116 X 3132-in.) to ash contents as low as 8 to 10% in dense-media devices, but washing the -3132-in. sizes to those limits presents more difficult problems, due mainly to the fineness of the material. This USBM investigation was conducted to determine the amount and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. The goal was to reduce the ash content to a level acceptable for industrial carbon uses, including electrode manufacture, which generally requires an ash content of 1% or less. While low-ash content is of primary importance in selecting industrial carbons, the amounts of other constituents are also important, including iron, silicon, titanium, nickel, vanadium, and sulfur. They were not considered in this work, since their occurrence in deashed anthracite has been studied elsewhere.4 The results of the present investigation were used to design a flowsheet, suggesting a method for producing ultraclean anthracite as part of conventional preparation practice, using dense-media vessels, crushers, pulverizers,

Jan 1, 1970

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By Morris Muskat

A theory is presented for calculating the performance history of complete water-drive systems producing from idealized stratified formations. The general equations are applied to systems where the permeability stratification is either of the exponential or linear type. Calculations were carried through for different degrees of permeability stratification, but with special emphasis on the effect of the mobility ratio between the produced oil and the invading water on the resultant performance. These results are also expressed graphically as curves for the initial water breakthrough recovery, for the different degrees of stratification, as a function of the mobility ratio, and of the composition of the produced fluid stream as a function of the cumulative oil recovery. For several typical cases the latter has also been plotted as a function of the cumulative oil and water throughflow. The general result is that when the mobility of the oil is lower than that of the invading water the channelling tendency resulting from the permeability stratification becomes aggravated as the higher permeability zones become flooded out. Situations of this type would obtain when producing low gravity or highly viscous oils. Conversely, if the mobility of the oil is high compared to that of the invading water, the flooding of the high permeability zones will lead to a retarding and choking effect, and the gross bypassing phenomena will be partially suppressed. These conditions would correspond to those of flooding high gravity or low viscosity oils. A discussion is given of the various basic assumptions made in the analysis, including that of ignoring the stripping phase of the production history as implied by relative permeability concepts. INTRODUCTION The physical ultimate recoveries from oil reservoirs are basically determined and limited by the physical oil displacement processes associated with the reservoir producing mechanism. In practice, however, the economic ultimate recoveries are further limited by the mobility of the reservoir fluids and the uniformity and continuity of the producing formation. In fact, it is the differential depletion between the component parts of the composite reservoir which ultimately determines the total recovery at the time of field abandonment. While this observation applies to both the solution gas drive and gravity drainage mechanisms, in which use is made only of the energy contained within the original oil-bearing reservoir, it is of even more paramount importance under operations wherein the energy associated with extraneous fluids provides the ultimate oil expulsion mechanism. Whether the invading fluid is the water from an edgewater drive, water injected for pressure maintenance, gas injected for pressure maintenance, or gas returned to the formation in a cycling program, it is often the continuity and uniformity of the producing section which will control the economic efficiency of the operations. The importance of the problem of reservoir non-uniformity does not, of course, lessen its complexity or the difficulties of its solution. In fact, these are inherently such that the concept of a "general" solution is virtually meaningless. About all that can be reasonably hoped for is the analysis of specific and well-defined types of non-uniformity which may give some degree of approximation to actual reservoir conditions. Since variations in the nature of the reservoir which depend only on the position along the streamlines will not lead directly to major differential depletion development within the reservoir, the types of non-uniformity considered thus far have involved stratification assumptions. That is, the producing section has been replaced by a multi-layer "sandwich," each uniform areally, and differing from the others only in its basic physical constants as to thickness, porosity and permeability. The fluid motion in the composite system is thus approximated by a parallel superposition of the independent fluid movements in the individual strata. For the specific application to cycling operations the theory of the effect of permeability stratification has been developed for both discontinuous' and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear' or probability3 functions. In all these studies complete dynamical equivalence was assumed between the injected dry gas and the displaced wet gas. The overall effective permeability of each stratum was therefore considered as constant and independent of the degree of invasion of the injected fluid. In the case of the displacement of oil by water, the assumption of dynamical equivalence between the water and oil will be strictly valid only by accident. Even if the oil viscosity should be the same as that of the water, the effective permeability to the oil in the presence of the connate water will in general be quite different from that of the water behind the water-oil interface flowing past the trapped residual oil. As a result the effective permeability for the stratum as a whole and rate of water invasion will change with time as the intrusion continues. The differential fluid motion in the individual strata will thus also vary with time. Qualitatively, it is easy to predict the resultant effects. If the permeability to viscosity ratio of the invading fluid exceeds that of the fluid displaced, the stratification and bypassing effect of the perme-

Jan 1, 1950

By Cresap P. Watson

ABOUT the time this magazine reaches its readers, Cresap P. Watson will celebrate his 53d birthday. If he spends that birthday at his West Los Angeles home, he won't be far, as distance is measured today, from Santa Barbara, where he was born on July 8, 1895. He is truly a member of a petroleum family; one brother, N. O. Watson, managed Royal Dutch Shell interests in Venezuela for years and is now general manager of the Caribbean Petroleum Co. at. Maracaibo; another brother, Rex, is vice-president of the Drilling and Exploration Co., while brother-in-law Ben Belt is an executive of Gulf Oil. His own life has centered in the petroleum industry since his first job in 1913 as camp cashier for a Mexican oil field at Tampico. Down on the isthmus of Tehuantepec he advanced to tool dresser and' production foreman for the company. The first World War interrupted his Mexican experience by transforming him into an artillery officer in France. Once the Army ceased to demand his services¬by then it was 1919-he returned to the task of furthering his professional career as agent for the Amerada Petroleum Corp. By 1927 he had reached the position in which he could be called an executive in the petroleum industry, having organized and become president of the Federal Royalties Co. His activities in local and national legislation affecting the petroleum industry increased as has his advocacy of the development of oil and gas fields under sound engineering and conservation principles through unitization or other co-operative forms of operation. Considerable amounts of his time go to the promotion of industry public relations.

Jan 1, 1948

By Strathmore R. B. Cooke, Iwao Iwasaki

RECENTLY spectrophotometry has been reported to provide a convenient technique for the rapid and reproducible determination of xanthate concentration in pulp solutions,12 and for a kinetic study of xanthate decomposition in acid solutions." Since the application of this analytical technique is feasible for those compounds showing pronounced light absorption maxima in the near ultraviolet region, it was deemed advisable to investigate the absorption spectra of some of the organic compounds that are used in flotation. It is known empirically that certain groups of atoms in an organic compound cause characteristic light absorption in the ultraviolet and near ultraviolet range, and the wavelengths and intensities of the corresponding absorption maxima are relatively independent of the nature of the remainder of the compound. The characteristic values of such groups, which are known as chromophores, are given in the literature.4,5 According to this information, many of the sulphydryl compounds are expected to show absorption maxima in the near or long wavelength ultraviolet region, whereas the saturated fatty acids and the saturated alkylamines do not. This article reports the absorption spectra of the six following types of sulphydryl compounds; mono-, di-(xanthate), and trithiocarbonates, dithiocarba-mate, dithiophosphate (aerofloat), and mercaptan. A Beckman DU quartz spectrophotometer was used to investigate the spectra in the wavelength region of 215 to 350mp. Materials: All the mono-, di-, and trithiocarbonates used in this investigation were prepared in the usual manner" from appropriate compounds obtained from Eastman Distillation Product Industries. The dithiocarbonates included the normal alkyl compounds from methyl to octyl inclusive, as well as the isopropyl, isobutyl, and isoamyl xanthates. Iodo-metric titration gave 99.7 and 99.5 pct purity for

Jan 1, 1958

By Andrew S. McCreath

THE manufacture of pig iron for conversion into steel by the Bessemer and open-hearth processes, is now one of the most important industries of the United States. It is necessary that iron intended for this purpose should be very pure, and especially must it be comparatively free from phosphorus. Great care must therefore he exercised in the selection of proper ores, flux, and fuel. Only such ores as are practically free from phosphorus can be used, and pure fuel is as much a necessity as pure ores; though hitherto iron men have paid comparatively little attention to this point. During the course of my work as chemist for the Second Geological Survey of Pennsylvania, I had occasion to examine some of the bituminous coals of the State for phosphorus, and the results obtained are so interesting that I venture to present them to the notice of the members of the Institute. The coals are arranged in geological order according to the different beds, and the table shows the percentage of phosphorus in the coal and also in the coke. The greatest number of specimens have been selected from the Pittsburgh bed, because it is the principal coal-bed of Southwestern Pennsylvania, and most of the mineral fuel which is mined along the Youghiogheny and Monongahela rivers, to be used in the coke ovens of the Connellsville region and in the blast furnaces and mills of Pittsburgh and its vicinity, and to be shipped to Western and Southern markets, comes from this bed. It will be noticed that many of the specimens examined contain

Jan 1, 1880

THE CHAIRMAN ( F. K. COPELAND, * Chicago, ,Ill.).-This is an interest-ing and very troublesome proposition to all of us. Ten or fifteen years ago, when the old-fashioned idea prevailed that a man was responsible for his own health and safety, that if anything happened to him it was his own lookout; we got along without this problem; but with the advent of accident compensation, with the agitation that there is all the time for pensions, sick benefits, and the responsibility of a company for the health of its employees, whenever you take a man on, that phase is becoming more and more important. One cannot afford to hire a man who is blind in one eye, even though he may have perfect sight in the other eye; if he loses that one eye, if lie becomes a total disability, the company is liable for the man's complete sight. Another thing that should make us particularly interested in this problem is the fact that the unions are very much opposed to it. One of the requirements of this steel unpleasantness is that the companies abandon their physical examination of employees. It is a very difficult problem to examine 400 or 500 men as intelligently as possible and decide whether a man on this or that side of the line is accepted. T. T. READ, Washington, D. C.-The United States. Bureau of Mines has in progress at the present time a study of the effect of underground atmospheric conditions on the safety and health of the workers. Im-proved methods have been employed and it is an excellent and ex-tremely valuable piece of research work.

Jan 12, 1919