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By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS CHESTER A. FULTON, Chairman CARROLL A. GARNER H. Y. WALKER WALLACE E. PRATT FELIX E: WORMSER PAUL D. MERICA, Consultant FINANCE COMMITTEE OF THE BOARD OF DIRECTORS ERIE V. DAVELER, Chairman WILBER JUDSON RUSSELL B. PAUL HENRY KRUMB, Consultant

Jan 1, 1944

By Castle. J. E., J. L. Gillson

In this chapter there is a wide difference in the meaning of some words used for rock and mineral names as defined by scientists and tabulated in the "Glossary of Geology and Related Sciences," published in 1957 by the American Geological Institute, and the meaning as used by the commercial producers of feldspar. It is necessary, therefore, to define these terms giving both the "scientific" and the "practical" definitions. There is no ambiguity about the name feldspar itself. This is a general term for a group of related minerals which are silicates of aluminum, combined with sodium, potassium and calcium. The feldspars are the most abundant minerals of the igneous rocks, and since these rocks make up the largest proportion of the earth's crust by volume (although not of the actual surface area of the continental land masses) the feldspars are the most abundant minerals of all. The igneous rocks themselves are classified on the basis of the variety of the feldspar present. The potash feldspars, which are called orthoclase and microcline, are the dominant minerals of the granites and syenites, and of their fine grained equivalents, the rhyolites and trachites. The plagioclase feldspars form an isomorphic series, of which the sodic endmember is called albite, and the lime endmember, anorthite. The members near the sodic end, albite, oligoclase and andesine are the characteristic feldspars of the granodiorites and diorites, and of their fine grained equivalents, the dacites, and andesites. These feldspars-orthoclase, microcline, albite oligoclase and andesine-are the feldspars used commercially. Labradorite, a member of the plagioclase group, in which the lime exceeds the soda in the chemical composition, is the common feldspar of the gabbros, anorthosites, norites, basalts and other so-called "basic" rocks. Although some attempts have been made to use labradorite as a commercial feldspar, none is now used except as an ornamental stone. The mineral anorthite is very rare. Since the feldspar in most of the common igneous rocks is relatively fine grained, and mixed intimately with other minerals, from which it can be separated cleanly only with difficulty, most masses of the common rocks cannot be used as sources for the feldspar contained in them. It is only the rarer types of rocks in which the feldspar is very coarse-grained, or ones containing very little of the iron-bearing minerals which are objectionable impurities in commercial feldspar, that are quarried to yield an acceptable product. The most widespread type of such a rock from which commercial feldspar can be produced, is that called "pegmatite." These rocks are dikes and bodies of irregular shape and of a size measured in feet or yards in most cases, rather than in miles. They are more commonly associated with granites, rather than with other coarse-grained igneous rocks. Many of them contain crystals of various minerals, including the feldspars, that are much larger than are found in the host rock, the granite, and in many there are large masses of feldspar that are sufficiently free from iron-bearing silicates so that products acceptable to the ceramic industry can be produced, in some cases simply by hand sorting. Most of this feldspar in pegmatites, however, does contain intergrown quartz up to 25 pct. Pegmatites are so important, not only as commercial sources of feldspar, but also of other minerals which are produced com-

Jan 1, 1960

By T. J. Whalen and Michael

The grain shape of the carbide in nickel-bowled ad cobalt-bonded titanium carbides was studied by microgiaphic examination, and the influcence of sintering atmosphere, sintering substl-after, ami the amount of metal binder on the grain shape was determined. If was found that the Carbide grain cross sections in the nickel and cobalt cermets ranged from round to angular, depending on the sintering conditions. The spheroidization of the carbides in both cobalt-bonded and nickel-bonded titanium carbides may be attribicted to oxygen. In the course of studies on titanium-carbide base cermets, various investigators have reported on the shape of the carbide grains, and it was noticed that grain shapes were obtained which were either spheroids, or polygons with rounded or square edges. It was also noted that the shapes of the carbide grains changed with time or composition. skolnickl showed that the titanium-carbide grains. after infiltration in vacuum with nickel tended to spheroi- dize with time. The titanium-carbide skeleton was located on a beryllia plate during infiltration. Gur-land,' who studied the microstructure of titanium carbide-cobalt compacts, showed that the carbide grains are round after 1 hr at 1450oC in a hydrogen atmosphere and angular after 7 hr at the same temperature. Goetzel3 has found that the carbide grains in compacts with a high binder content. 40 to 60 pet. tend to be spheroidized. whereas Blumenthal and silverman4 pointed out that the higher binder contents could yield either round or rectangular grains with rounded edges. depending on the nature of the binder. It is the purpose of this paper to present experi-

Jan 1, 1961

By Wayne E. Tuomi

The mining industry is faced with a pressing problem; that is, to develop more efficient methods of extraction, handling and upgrading-techniques that will do the job faster and better than ever before. New techniques require new machines, or applications of new and improved materials that can be used to modify and improve existing machine and equipment designs. The traditional approach has been to increase productivity by increasing equipment size. Prognostication indicates that the trend toward larger equipment sizes and capacities will continue as one answer to the challenge imposed by future increases in mineral demands. But what is the limit on the continued growth of equipment size? Until about 1930, there was a very definite limit-a limit imposed by the strength of the steels and the power plants then available. The equipment engineer had come to an impasse: even though it was easily possible, for instance, to triple the size of a bucket, it had become impractical to correspondingly enlarge the boom, the counterweight, and the power plant.

Jan 3, 1967

By Gray L. L., Max Littlefield, Godbold A. C.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By Max Littlefield, Godbold A. C., Gray L. L.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By S. G. Bankoff

INCE1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. [ ] In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (-200 mesh) and 50 c.c. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments [c] through g are more insoluble than lead carbonate, therefore should prevent the formation of lead carbonate on the galena surface. In experiment [i] the calcium oxalate, which presumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments [j] through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1941

By John V. Beall, William F. Haddon

A long the mighty Andean Cordillera, there is splendor beyond imagination-in the natural beauty of the mountains and in daring engineering and lavish investment in the mines. This is the story of the great copper mines of Chile and Peru. Each mine has a special quality which has tested the physical and spiritual resources of the founder. In the early days of the older mines, the mining engineer of song and story was more the rule than the exception. He was physically tough, ingenious and a leader of men. In the current political and social environment of Chile and Peru, the foreign contract mining engineer is still needed; but he must be a different type of man. To John J. Selters at Cerro's Rio Blanco, the principal ingredient is still "toughness," but it is "toughness of mind" that is needed. "He probably should be a teacher." The copper mines are not new. They were, almost without exception, worked by Indians (La Exotica might prove the rule), and later by the intrepid Spaniards. Modern mining began after the turn of the century. In Chile, the first of the big ones was the Braden Copper Co. founded on the El Teniente deposit. This development was followed by Chile Exploration Co. at Chuquicamata and Andes Copper at Potrerillos. These properties have been developed over the years by vast expenditures of money and a monumental amount of labor. None was free of technical problems-metallurgy at Chuqui, marginal grade of the old mine at Andes, avalanches and the great fire at El Teniente. The evolution which has brought the established mines of Chile, and the new ones coming on stream, to their present state of development is in reality the work of wonders of input-money, engineering and responsible management in an atmosphere of political stability. Without any one of these, the result would have been failure.

Jan 11, 1969

A dinner was given to Ambrose Swasey by the United Engineering Society, at the Engineers' Club, on November 14. Those present -included -twenty-one presidents and past presidents of the Founder Societies. Charles F. Rand, President of United Engineering Society, presided. President Robert S. Woodward, of the Carnegie Institution of Washington, and Dr. Robert W. Hunt, of Chicago, made addresses to which Mr. Swasey responded. Dr. Michael I. Pupin, Chairman of Engineering Foundation, made the closing address. The evening was marked by the high character of the addresses, inspiration for grave duties lying before the engineering profession, and by the spirit of good fellowship. Among the seventy-two persons present were the following members of the Institute: E. E. Bartlett, William N. Best, J. Parke, Channing, C. R. Corning, F. C. Cottrell, J. V. Davies, J. V. N. Dorr, H. S. Drinker, Karl Eilers, H. M. Howe, A. C. Humphreys, Robert W. Hunt, Wm.. B. Jackson, D. S. Jacobus, J. H. Janeway, J. E. Johnson, Jr., John Johnston, George F. Kunz, Edwin Ludlow, Philip N. Moore, Fred'k. H. Newell; Wm. H. Nichols, H. Hobart Porter, Charles F. Rand, R. M. Raymond, .Jesse M. Smith, E. Gybbon Spilsbury, Bradley Stoughton, . Joseph Struthers, Benj. B. Thayer, Wm. H. Wiley, S. T. Wellman.

Jan 1, 1919

By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart's model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison's case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison's classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By George Rice

THE subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on bumps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free' from folding and faulting.

Jan 1, 1935

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.' Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy's law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f'(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f'(S) can be calculated. It turns out that the experimentally derived f'(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By George Burrell

J. S. HALDANE, M. D., F. R. S., Oxford, England (communication to the Secretary?).-The valuable paper of Messrs. Burrell and Gauger is of special interest to me as, through the courtesy of the management, I had an opportunity of visiting the Portland mine, Cripple Creek, in 1911, in connection with the investigations on acclimatization to high altitudes, carried out on Pike's Peak, near Cripple Creek, by Professors Yandell, Henderson and Schneider, Dr. Douglas and myself.1 The analyses of one or two samples of the vitiated air were entirely confirmatory of those of the authors. A fatal accident owing to two men being lowered down a shaft filled with the gas had occurred in a neighboring mine just before our visit.

Jan 12, 1916

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein' and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y' phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y' and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951

By F. L. Clerc

THE lead and zinc region of SW. Missouri is interesting, not only by reason of the value of its output, which ranges in the neighborhood of ten million dollars a year, but even more because of the facilities which it offers for the study of certain forms of ore-deposits, of which the loci and genesis are somewhat obscure. Although the mineral species found in the region are few and of common occurrence, crystallization has taken place on a generous scale, and unusual forms abound in many combinations, presenting examples of pseudomorphism, paragenesis, metasomatic replacement and the action of mineral-depositing and mineral-dissolving waters. For the mineralogist, lithologist, and specialist in certain lines of metamorphism, it has peculiar attractions, while the systematic geologist will perhaps find its chief claim to attention in the simplified problem it presents, in the study of ore-deposits. In addition to the phenomena above enumerated, it presents instances of well-developed comb-structure in the ores, fissures and faults, and slickensides-features usually associated with extensive movements in the earth's crust, and believed by some authorities to prove the deep-seated origin of the ores. In connection with these occurrences, the absence of all igneous rocks from this region is noteworthy and significant. For that reason, the simplified case presented by the Joplin region, from which these rocks have been eliminated as a factor, is specially valuable. Having had unusual opportunities to watch the development of this district, I have been deeply interested in the bearing of the revelations of the Joplin mines upon questions of universal importance to the science of ore-deposits ; and it was to my great regret that the project of a meeting of the American Institute of Mining Engineers at Joplin, proposed in 1892, was

Mar 1, 1907

By V. M. Karve, K. K. Majundar, K. V. Viswanathan, J. Y. Somnay

The effect of calcium, magnesium, iron (both ferrous and ferric) and aluminum ions, which are commonly encountered in a typical beryl ore, was studied in the flotation of pure beryl, soda-feldspar and quartz. The vacuumatic flotation technique was employed. With sodium oleate as collector and in the absence of any activator, beryl floated in a pH range of 3 to 7.5, whereas feldspar and quartz did not float at any pH up to 11.5. The pH range of flotation increased in the presence of the ions studied. With calcium and magnesium ions beryl floated from 3 to 11.5 pH and beyond, soda-feldspar floated beyond pH 6 and quartz floated beyond pH 8. Ferrous ion activation was found to be similar to that of calcium and magnesium. Activation by ferric and aluminium ions was found to be complex and the lower and upper critical pH for all the three minerals was around 2 and 10 respectively. These studies indicated the possibility of separation of beryl from feldspar and quartz even in the presence of calcium, magnesium and ferrous ions between pH 4 and 6. Flotation tests on a mixed feed of pure minerals in a 10 g cell revealed that beryl can be selectively floated from feldspar and quartz if ferric ion is reduced to ferrous state or if it is complexed. Beryl occurs mostly in pegmatites, and hence is associated with feldspar, quartz and micas and small amounts of other minerals such as apatite and tourmaline. The separation of beryl from these minerals is difficult because all the silicates accompanying beryl have more or less the same physical properties. Specific gravities of beryl, feldspar and quartz are 2.70, 2.56 and 2.66 respectively. Electrostatic separation has been suggested but no work has been reported. ' The adsorption of sodium tri-decylate tagged with Cl4 on beryl, feldspar and quartz reveal similarity in surface properties. Much work has been reported on the flotation of beryl from ores, either directly or indirectly as a by-product, but little is known about the fundamental aspects of beryl flotation. Kennedy and O'Meara3 laid emphasis on prior cleaning of the mineral surfaces with HF. Mica is removed first by flotation of beryl with oleic acid, around neutral pH. Runke4 introduced calcium hypochlorite conditioning in a final separation stage for activating beryl in a mixed beryl-feldspar concentrate, and after washing to remove the hypochlorite, floated beryl with petroleum sulphonate. The Snedden and Gibbs5 procedure is somewhat similar to that of Kennedy and O'Meara. Emulsified oleic acid is used as collector. Recently Fuerstenau and Bhappu6 studied the flotation of beryl, feldspar and quartz with petroleum sulfonate in the presence of activators and stressed the importance of iron in the flotation of beryl. From the studies conducted in this laboratory, it was found that feldspar and quartz as such do not float with sodium oleate, but in practice selective flotation of beryl from feldspar and quartz in an ore is found to be impossible with sodium oleate as collector. A glance at the chemical analysis of typical beryl ore indicates the presence of several ions like Ca ++, Mg++, Al + + + and Fe+++ in abundance and Ti++++ and Mn++ in traces. Hence, in an attempt to explain the behaviour of feldspar in the beryl flotation, the effect of Ca++, Mg++, Al+++ and Fe+++, which are known as gangue mineral activators7'8 has been investigated. Materials and Methods: Lumps of beryl ore (hand picked) were boiled with 10% sodium hydroxide and washed with distilled water. They were further boiled many times with 10% hydrochloric acid till no positive test for iron was obtained with ammonium thio cyanate. This was followed by thorough flushing with double distilled water. The lumps were crushed in a porcelain mortar and pestle under water. The minus 65 + 100 mesh fraction was used for testing and was always stored under distilled water. Pure feldspar and quartz were similarly prepared and the minus 65 + 100 mesh fractions collected. Inorganic ions tried as activators were ca++, Mg++ , Fe++, Fe ++ and A1 +++ . Calcium nitrate, magnesium chloride, ferrous ammonium sulfate, ferric ammonium sulfate and aluminum nitrate of G.R.E. Merck grade were used. B.D.H. technical grade sodium oleate was used as a collector. The vacuumatic flotation technique developed by Schuhmann and Prakash was used for studying the effect of pH on flotability. 7 The indications given by this work were confirmed by using 10 g miniature cell.'

Jan 1, 1965

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

Jan 1, 1902