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By Lo-Ching Chang, J. Chipman

The perennial and increasing interest in the chemical behavior of steelmaking slags has led to numerous attempts to formulate the thermodynamic properties of these solutions. The classical view is that of a solution of the component oxides in which certain acidic oxides are more or less completely held in combination with basic or metallic oxides, the nature of the interoxide compounds being derivable from the chemical behavior of the slag or from the mineralogy of a solidified specimen. The known electrical conductivity of slags has pointed to the existence of ions in the solution and a number of attempts have been made to account for the observed facts of slag behavior on the basis of a theory of complete ionization of the solution. It is the purpose of this paper to examine, in the light of ionic theory, a number of recently published series of data on slag-metal and slag-gas equilibria, with the purpose of obtaining a more complete or more satisfactory generalization than has been possible on either of the single bases of simple compound formation or complete ionization. The attempt to formulate the ionic constitution of a complex solution is fraught with many uncertainties. An ion is not something that can be plucked from the solution and examined in detail, nor can its true formula be determined with certainty by any single experimental method. In attempting to express the composition of a slag by various ionic formulas it can be expected that alternative hypotheses of essentially equal merit will present themselves. In the present state of early development of the ionic theory of slags, it may be necessary to make some rather arbitrary choices of ionic formulas in the absence of su- cient information to yield complete certainty. Acids and Bases The classification of slag-forming oxides as acidic or basic apparently dates back into the days of Berzelius. It is difficult to see how the concept could have originated in the early twentieth century when it was fashionable to define an acid or a base as an aqueous solution containing hydrogen or hy-droxyl ions. It is, however, entirely consistent with the modern and more general theory of acids and bases. In this theory, as originally formulated by G. N. Lewis,' a basic molecule is one that has an electron pair which may enter the valence shell of another atom thus binding the two together by the electron-pair bond. An acid molecule is one which is capable of receiving such an electron pair into the shell of one of its atoms. The acid, the base, and the product of neutralization may be either ions or neutral molecules. The product of such a reaction may itself be a base or an acid if it is further capable of giving or accepting an electron pair. Thus a base is a donor of electrons, an acid, an acceptor. In oxide slags the typical and ever-present base is oxide ion, 0-—. In behavior and in importance it is analogous to hydroxyl ion, OH-, which is the typical base of aqueous solutions. There is nothing in the chemistry of slags which is quite analogous to the acid H30+ in aqueous solutions. This is not surprising for in slag systems there is nothing which can be designated as a solvent and no ubiquitous positive ion. The chemistry of slags is in fact more complex than the chemistry of aqueous solutions and the concepts which must be evoked in its study are correspondingly broader. In seeking a basis for a classification of slag-forming oxides as basic or acidic it must be remembered that these terms are not absolute but relative. A substance which acts as a base toward a second substance may act as an acid toward a third. This is less likely to happen among strong bases or acids than among the weak ones; there are numerous examples of weak acids which under the influence of a stronger acid behave as weak bases. Such substances are called amphoteric. A classification of the glass-forming oxides has been proposed by Sun and Silverman² and further developed by Sun3 in which the oxides are arranged in order of decreasing acidity or increasing basicity, each substance being potentially capable of acting as an acid toward substances below it in the list and as a base toward those above it. It is based upon the relative strengths of the metal-to-oxygen bond as determined by the energy required to dissociate the oxide into its component atoms.' Data are available for computation of this energy, at least approximately, for the oxides of slags and glasses. In general those oxides from which it is most difficult to remove the positive atom are the strong acids while those in which it is most loosely held are the strong bases. It is in the latter, of course, that formation of oxide ion occurs most readily as, for example, in CaO which in solution ionizes to form the weak acid Ca++ and the strong base O—. The order of arrangement found by Sun is shown in the first column of Table 1, to which have been added the data for

Jan 1, 1950

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship' to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,' using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager's extenbion of Fick's first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

By Elmer W., Pehrson

NOT much serious consideration was liven to the military aspects of raw materials before World War 1. Following the outbreak of war in Europe in 1914, however. this situation was promptly changed. Disruption of allied shipping and German submarine warfare soon cut off a substantial part of the material the United Staten was accustomed to receiving from overseas. At the same time, raw material requirements rose rapidly as the tempo of industrial preparedness was stepped up in anticipation of war. By April 1917, when we entered the war, serious shortages threatened and consideralde attention was being given to our "deficcient" raw materials. The term "war mineral," began to appear after we became active combatants. But there is no evidence that "strategics" and "critical." as now used, had entered the lexicon of our raw materials experts during the last war nor were there apparently any officially recog¬nized list or definitions of what con¬stituted war materials. According to G. A. Roush in his book, `'Strategic Mineral Supplies," C. K. Leith, while serving as mineral advisor to the War Industries Board. compiled the first unofficial list of deficient minerals in 1917.

Jan 1, 1944

By Henry Morris

AS STATED last year, in a similar review by David White and the author, any review of the petroleum industry purporting to cover such a wide field can only mention the principal facts. This incompleteness is necessitated not only by the limitations of space, but by the delay in receiving detailed information. The principal feature of the year, in Europe, was a material increase in the consumption of petroleum products, and a notable decline in prices. Although there we relative increases in production in Roumania and Poland, the total did not by any means keep pace with the increase in consumption, which, as usual, was supplied "from America and both the Near and Far East. The interest in Asiatic production, as usual, centers around the Persian fields, which, according to the annual report of the Anglo-Persian Oil Co. published at the close of last year, it was estimated would amount to 3,775,000 tons by the close of the fiscal year, March 1, 1924. Russia also showed an increase in production. In Africa there was nothing of outstanding interest in production, although Egypt showed a decrease and the goverment refinery at Port Said was closed.

Jan 3, 1924

The Committee on a Standard Gauge have been constantly engaged, since their appointment, in the duties assigned to them.§ They have corresponded with different persons interested in the manufacture and use of gauges in this country, and have received from several of them important information. They have also entered into correspondence with the governments of England, France, Gerniany, and Russia through their Consuls, ant1 with Austria directly. The Consuls of Germany and France

Jan 1, 1879

By W. N. Logan

THE petroleum industry in Indiana made no extraordinary progress during the year 1924. The surplus stock of crude, brought about by the production of 732,407,000 bbl. in the United States in 1923, as against a production of 557,531,000 bbl. in 1922, had its effect on prices though there were slight advances. These advances were more than offset by the continued high prices of labor and materials. TRENTON OIL DEVELOPMENT The principal development of the year occurred in the Hotmire pool of the Ridgeville district in northeastern Indiana. This pool lies partly in the southern part of Jay County and partly in the northern part of Randolph County. The oil is obtained from the upper horizon of the Trenton. During the past year, about 30 wells were drilled, 21 of which were productive. An attempt to extend the Hotmire pool to the northeast resulted in the discovery of a gas-producing area near the center of Pike township in Jay County; 10 wells have been drilled 4 of which produced oil. The Harvey Orr No. 1 produced 900,000 cu. ft. of gas per day.

Jan 3, 1925

By J. W. Cloud

years ago upon the effect of having the rails always rolled in the same direction, and also of having them rolled backwards and forwards, and showed that under the latter course there were of necesshy weak spots somewhere near the centre of the rail, yet in all this discussion the methods of rolling have been passed by almost in silence. Mr.. Sandberg in his paper mentions the idea of using a regietering dynamometer attached to the punching machines, and of det.erminit~g the quality of the metal by the resistance which is shown. I think the' first idea of this kind was published by Professor Langley, then of Pittsburgh, who, while making some investigations for Mesrs. Miller, Metcalf and Parkin, announceti as tile result of a series of dynamometric experiments that abrasive resistance was the term which should be wed in regard to steels of different wearing qualities. I have had extremely delicate dynamometers attached to the instruments of precision with which I am making the iuvestigation on the fatigue of metals, and hope soon to communicate the results of the iovegtigation- made with them to the Institute. I wish again to call attention to the fact that we are wing the words " hardener " and " hardness " without any real idea of the meaning of these words. When we say hard and soft, as we have hen constantly doing during this discussion, is it quite sure that every one has exactly the same meaning in his mind ? Certainly, when hard is used in distinction from soft*, we mean not the capacity of wear, but the capacity of resistance to peuetration, to fracture, or some other resistance, and do not always meau the capacity of resistance to abrasion or crushing, which the discussion would sometimes seem to imply were the only qualitiw requisite to constitute a god rail. J. W. Cloud, Altoona, Pa. : I would call the attention of the Institute to the title of Dr. Dudley's interesting and valuable paper, —" The Wearing Capacity of Steel Rails in relation to their Chemical Composition and Physical Properties." Here are two separate and distinct questions: lst, The wearing capacity of steel rails in relation to their chemical content; and 2d, the wearing capacity of steel rails in relation to their physical properties. The discussion has been almost exclusively confined to the former question, on which there may be many differences of opinion in matters of detail without greatig affecting the result. The latter

Jan 1, 1881

By R. W. Hunt

The old plan was to increase every part of a rail much in the same proportion. But each part should be in proportion to what it ha.; to do. The head should be deep in proportion to tile amount. of traffic and the lowness of the rate of interest on its cost. The body need only he strong enough to carry the head after it is well worn down, and that deperlds on the weight of the machinery, and in the case of steel has little to do with the volume of traffic, except SO far as that affects weight of machinery. Ad on most railroad systems, the same niacliinery is used on main lines with heavy traffic, and bra11ct:es with light, I suggested in 1874 that each systern adopt the same body of rail for both, and make the head deeper on the main lines, shallower on the branches. This plan was adopted on the Pennsylvania Railroad. Bandberg seems to recognize this in his patterns of 1878. E. W. HUNT, TRoy, N. Y.: Again Dr. Dudley preaents to our cousideration a series of most carefully conductetl experiments, and ~llile I fully appreciate the labor and thought this work has cost him, I must still hesitate to accept his deductiono. This paper dilliirs from the previous one in that it denls esclrieively with the wearing qualitiei. of steel rails. Dr. Dudley gives his reason for this change in the following statement: " With the improvement in maintenance of way which has characterized the Pennsylvania Railroad during the last five or six yearn, the remova1 of rails from the track from the first two of these causes (i. e., broken and crushel), has, if I am right, quite notably diminished. This certainly is true with regard to broken rails. And if, as time advances, the number of crushed rails shall diminish, both because of the continued improvement in maintenance of way before referred to, and because, owing to improved and better methods at the steel works, there are fewer crushed rails caused by physical defects in the steel, the question of the wearing capacity of steel rails obviously becomes the allimportant one." Certainly the condition of the roadhd has much to do with mils brealring, crushing, and wearing. If the Pennsylvania and other railroads have done and are doing their part, Dr. Dudley oourteously admits that the steel works have performed part of theirs. But as far as I am informed, the formulas which they have used have been and are still quite wide of the one he continues to recommend. The rails which are not breaking or crushing to so great an extent as formerly, contain higher percentages of both carbon and manganese.

Jan 1, 1881

By L. C. De Jong, J. F. Shirley, M. L. Campbell

The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes 36,500 tons of ore daily containing between 0.50% and 3.00% copper. The molybdenite content in the ore also varies greatly, ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03 % molybdenite. The three basic problems that plague the opera- tion of any molybdenite recovery plant are all present at Toquepala in large measures. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molybdenite plant metallurgist, there are four distinctive chalcopyrite concentrates and, at least, an equal number of chalcocite concentrates treated in the molybdenite recovery circuit. The various types of concentrates are distinguished mainly by their mineral content and how effectively the copper minerals are depressed by the different reagents used in the circuit.

Jan 9, 1967

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By Lawrence B. Wright, Lester G. Morrell

ON the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest was evidenced in this district until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine [t] in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1938

By Lester C. Uren

Petroleum occurs, in nature, as a fluid saturating the pore spaces between the grains of porous rocks or aggregations of rock particles such as sand, sandstone, conglomerate, shale, limestone, etc. The oil, under the influence of gas pressure, hydrostatic pressure, gravity, earth pressure, and, perhaps, other natural forces, is caused to flow through the porous "reservoir rock1' into wells penetrating the stratum in which the oil occurs. The principal moving force is the pressure of dissolved or occluded natural gas within the oil, though this force is assisted by gravity and by the hydrostatic or buoyant pressure of ground water about the edges of the "pool." The wells, providing outlets to the surface, are centers of reduced pressure and the flow of rock fluids into a particular well is usually an expression of the difference in pressure existing between the space within the well and that of the stored oil within the reservoir rock. The greater this differential pressure, the more rapidly will oil flow from the source rock into the well. Opposing movement of the oil from the reservoir rock into the well are certain natural forces related to the rock structure, such as pore friction and capillarity, and certain others related to the physical properties of the oil, such as viscosity and adhesion. The differential pressure between the well and the boundaries of the area drained by it must be sufficient to overcome the forces opposing flow if there is to be movement of oil into the well. If by any device the resistance to movement of the oil may be reduced, the oil will flow into the well at a more rapid rate and the effective area of drainage will be increased.

Jan 1, 1925

By Halbert Powers Gillette

In every chemical reaction heat is either developed or absorbed, and this plus or minus heat of formation is as definite in quantity as the weights of the reacting elements. In this paper I shall show that each chemical element and each chemical radical has its own definite heat-valency,—a fact which, so far as I know, has hitherto escaped the attention of investigators, but, I feel sure, will be admitted after the demonstration here given, and may lead to some practical conclusions of value. When Berthelotys " law of maximum work " was found to have so many inexplicable exceptions, the pendulum of a scientific theory swung away from a recognition of the truth underlying that proposition; and this reaction went so far that not only has thermal chemistry been relatively neglected by recent investigators, but it is not uncommon now to find textbooks on physical chemistry which practically ignore all that Thomsen, Berthelot and others have done. To this temporary tendency of thought I attribute the failure to recognize the principles herein announced and explained. Not long ago, while studying tables of the formation-heat of various salts, I noticed that in this respect all potassium salts in solution differ from the corresponding sodium salts by 9.3 cal.1 I found also that similar differences exist between other salts, not only when the basic radical is varied, while the acid radical remains constant, but also when the acid radical is the variable. Thus chlorine salts in solution differ from bromine salts in this respect by 10.9 cal. Upon further study, I found that Thomsen had noted similar constant differences, but, so far as I can ascertain, he appears to have attached no great significance thereto.

Jan 1, 1904

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

The present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.l A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various ¦ types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. Development of the Process The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton. Until the method of continuous production of manganese by electrolysis was perfected by SheltonZm4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solutioil containing 2 5 grams manganese per liter as manganese sulphate and zoo grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.0j gram iron per liter as ferrous sulphate followed by oxidation with manganese dioxide, and aeration, which precipitated the iron as ferric hydroxide. The solution, free from iron

Jan 1, 1944

By J. S. Osoba, J. G. Richardson, F. M. Perkins

Laboratory experiments have shown profound diffcrences in the behavior of so-called "fresh cores" from the East Texes field and of the same cores after ex~ractio~l with organic solvents. The residual oil satura/ion remaining after waterflooding fresh cores was appreciably lower than the corresponding saturations after flooding extracted cores. This behavior was also reflected in the water-oil relative permeability-saturatiorl relations, which were more favorable for high oil recovery from the fresh cores. These differences were evident not only in the amount of residual oil left after wafer flooding, but also in the saturation water remaining in the core after displacernent by oil. Residual water saturation after displacernetzt of water by oil was higher in the fresh cores than in the extracved core,. Capillary pressure-saturation relations were also different for the fresh crnd extracted cores. Imbibition experiments indicated that both fresh and extracted Bast Texas cores imbibed water spontarteOLISIY, but- the rate of imbibition of water was higher for samp1es after. extraction than it was for fresh core. material. INTRODUCTION Several years ago a series of waterflooding tests was made in the laboratory on a number of Woodbine core samples from the East Texas field. These samples had been stored in containers open to the air and were extracted with organic solvents before they were subjected to the laboratory tests. After water flooding, the residual saturation of kerosene, which was the oil used in the tests, was found to average about 30 per cent. This saturation was higher than expected. In investigating the circumstances which might have been responsible for such a high residual oil saturation, attention was given to possible changes in wetting properties of the rock brought about by the procedure employed in extracting the cores. Preliminary results indicated that the explanation for the high residual oil saturation lay in the wetting behavior of the cores, though what effect extraction had on this behavior was not clear. In consequence, the work described in this report was undertaken in an attempt to investigate the mechanism responsible, and to ascertain the actual residual oil saturation to be expected in the reservoir after water flooding. It was soon found that there were profound differcnces in the behavior of so-called "fresh cores" from the East Texas field and of the same cores after extraction with organic solvents. These differences were evident not only in the amount of residual oil left after water flooding, but also in the saturation of watet remaining in the core after displacement by oil. The complete explanation of this behavior is not yet apparent. The description of work and results described in following sections, therefore, must be considered as an interim report presenting facts which must await additional information before they can be fully interpreted.

Jan 1, 1956

By Walter Knox, Charles H. Sawyer

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944