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By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By N. H. Fisher

Geographical Distribution 'he most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig I). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation Ltd., of Melbourne, on Stradbroke Island, and in other places. Physiography Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 56 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, upto 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1949

By A. T. English

X-ray dif action techniques were used to investigate ordering and domain coalescence for the B2 (CsC1) superlattice in this alloy. Essentially complete disorder is obtainable by drastic quenching. isothertmal ordering occurs very rapidly at temperatures between 565° and 680°C, only a few seconds being required for development of substantial long-range order. A very fine antiphase dormain structure, found in samples annealed for short times, undergoes coalescence with further annealing. Domain "size" is found proportional to (t)1/2 . This Yate law can be derived by adapting the formalism of Hillert's analysis 01- metallurgical grain growth. For this Purpose the material is descvibed in terms of a "Swiss-cheese " structure, consisting of two multiply connected, mutually intertwined domain volumes. The observed activation enevgy for coalescence, 70 kcal per g-atom, agrees with an estit~lated value ,for volume diffusion in disordered rrzaterial. It is suggesled that the experimental value vejlects the substantially disordered environment of mobile vacancies located in the moving antiphase domain boundary. The alloy Fe-Co-2V is bcc below about 900'C and orders into a B2 (CsC1) superlattice below about 730c It has important applications in magnetic components, including many requiring extensive cold rolling.* example, Marcinkowski and Brown6 observed a re1atively small as-quenched domain size of about 250Å in B2 Fe3A1. Since there appear to be no published data on domain coalescence in B2 alloys, this process was studied in detail. MATERIALS AND EXPERIMENTAL TECHNIQUES A commercial high-purity alloy, nominally 49 Fe-49Co-2V, was obtained from the Arnold Engineering Co. in the form of cold-rolled sheet 0.004 in. thick. Samples were annealed for 1 hr at 800°C in dry H2 to produce disorder and quenched into iced brine. They were then annealed in a nitrate-nitrite salt bath for various times at temperatures between 525° and 625°C. Estimates of the LRO parameter S and the APD size D were made using established X-ray diffraction techniques. Superlattice peaks are best observed using CoKa radiation, for which the value of (fFe-fCo) is maximized. Peak-to-background intensity ratio was improved by filtering CoKß from the incident beam to eliminate sample fluorescence, and by using a pulse-height analyzer. The LRO parameter S was computed from the ratio of integrated intensities I 100/I 200- Owing presumably to systematic errors associated with the presence of crystallographic texture and X-ray extinction, only rough agreement was obtained between experimental and theoretical (absolute) intensity ratios. For this reason certain experimental refinements (e.g., use of balanced filters) were considered superfluous and were omitted. Emphasis was placed on maximizing intensity in order to reduce the time taken to accurately determine the contour of the very small (loo), peak. This was done by point counting 105 counts at appropriate intervals. Background intensity averaged about 1200 cps.

Jan 1, 1967

By G. W. Lester, T. J. Nowak

The paper presents a practical method of utilizing pressure fall-off data obtained when a water injection well is shut in for determination of: (I) the static reservoir pressure, (2) the potential water injective capacity (md-ft) of the formation, and (3) the formation damage (skin effect) surrounding the wellbore. In the development of the method, equations are presented which give The theoretical background for predicting the behavior of water injection wells. Certain physical factors which limit the application of the method are discussed. The procedure and the relevant precautions in obtaining the data are discussed. A sample analysis and computation from an actual pressure fall-off curve is illustrated. Fintrlly, general characteristics of pressure fall-off curve! obtained in several reservoirs are presented. INTRODUCTIO N Theoretically, in an injection well the flow of water into the formation will continue as long as the sand-face pressure is greater than the reservoir pressure. However, in practice, engineers have observed that upon stopping injection and opening the wellhead to atmospheric pressure, some wells backflow water for time intervals ranging from several seconds to several hours although the sand-face pressure, as calculated from the hydrostatic head, is considerably greater than the static reservoir pressure. Further, field observations indicated that upon shutting in a water input well, the wellhead pressure does not drop off immediately, but a pressure decline occurs lasting from several seconds to several days. These observations make it evident that when an input well is shut in, a residual pressure lingers in the vicinity of the wellbore which is greater than the average reservoir pressure. This residual pressure declines first rapidly, then more slowly, to the static reservoir pressure: therefore, it is called transient back-pressure or pressure fall-off. The first step in investigating the mechanism of pressure fall-off is to establish what general conditions are necessary for its occurrence, and to this end, Dickey and Andresen1 have presented a qualitative explanation describing the mechanism. They point out that the formation pressure gradient in the vicinity of the well does not disappear immediately when the input well is shut in, as if the system were filled with a totally incompressible fluid, but it is maintained by the expansion of the compressible fluids and by the elasticity of the formation. In such a compressible system the decrease in pressure is possible only to the extent that the water front continues to advance until the pressure is equalized. The principal aim of this paper is three-fold; namely. (1) to present a theoretical quantitative analysis of pressure fall-off data, (2) to present an application of the developed theory to field data, and (3) to discuss the general characteristics of actual pressure fall-off curves. Under (I), theoretical equations dealing with such factors as compressibility of the fluid-reservoir system, mobility of the fluids and certain physical restrictions that

Jan 1, 1956

By B. H. Sage, W. N. Lacey

The results of an extensive experimental program relating to the effectiveness of gravel screens have been correlated. The factors considered in some detail include gravel size and condition of packing, sand size and size distribution, fluid velocity, fluid viscosity, and thickness and arrangement of grave! screens. Good agreement between calculated values based upon probability considerations and experimental results relating to the influence of the thickness of the gravel screen was obtained. All of these factors are treated in the correlation in order that their influence may be taken into account in ascertaining the characteristics of an effective gravel screen for a particular set of conditions. The details of the experimental program are not given in the present paper but a description of generalized behavior and typical experimental results are recorded in graphic form. Introduction Gravel screens have been placed in water and oil wells for a number of yearsl,2,3 with the dual objective of increasing the productivity and decreasing the entrance of sand into the well bore. An understanding of the factors controlling the effectiveness of gravel screens in this connection is of industrial interest because it will lead to the proper selection of gravel. Some of the fundamental considerations involved in the migration of sand through a coarser body of porous materials were investigated by Coberly and Wagner4 and further experimental work has been carried out by Gumpertz.5 Apparently the pertinent phenomena are somewhat complex and are influenced by many variables. The present paper deals with the prediction of the behavior of gravel screens under the conditions encountered in practice but does not attempt to discuss the experimental methods or results that were obtained as a background and upon which the prediction is based. Influence OF Gravel Screens upon Productivity The use of a gravel screen may increase the productivity of a well by increasing its effective diameter, and this constitutes one of the objectives of its use. The permeability of most gravels and coarse sands that are employed in practice is so large compared to that of the sand in place that relatively little loss in production rate will arise from the use of material fine enough to cause the desired resistance to sand migration. For example, in Fig. I is depicted the approximate variation in the permeability of closely sized spherical gravels under the conditions of packing likely to be encountered in screens. The dotted lines indicate the variation that might be found because of differences in packing. It should be realized that the permeability is not a single-valued function of the average grain diameter but is related to a large number of factors, including the size, the size distribution and the shapes of the particles. However, Fig. I does permit a rough estimation of the permeability of closely sized spherical gravels and shows that the permeability with even the smaller particles is very large compared to that of most petroleum production horizons.

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By W. N. Lacey, B. H. Sage

The results of an extensive experimental program relating to the effectiveness of gravel screens have been correlated. The factors considered in some detail include gravel size and condition of packing, sand size and size distribution, fluid velocity, fluid viscosity, and thickness and arrangement of grave! screens. Good agreement between calculated values based upon probability considerations and experimental results relating to the influence of the thickness of the gravel screen was obtained. All of these factors are treated in the correlation in order that their influence may be taken into account in ascertaining the characteristics of an effective gravel screen for a particular set of conditions. The details of the experimental program are not given in the present paper but a description of generalized behavior and typical experimental results are recorded in graphic form. Introduction Gravel screens have been placed in water and oil wells for a number of yearsl,2,3 with the dual objective of increasing the productivity and decreasing the entrance of sand into the well bore. An understanding of the factors controlling the effectiveness of gravel screens in this connection is of industrial interest because it will lead to the proper selection of gravel. Some of the fundamental considerations involved in the migration of sand through a coarser body of porous materials were investigated by Coberly and Wagner4 and further experimental work has been carried out by Gumpertz.5 Apparently the pertinent phenomena are somewhat complex and are influenced by many variables. The present paper deals with the prediction of the behavior of gravel screens under the conditions encountered in practice but does not attempt to discuss the experimental methods or results that were obtained as a background and upon which the prediction is based. Influence OF Gravel Screens upon Productivity The use of a gravel screen may increase the productivity of a well by increasing its effective diameter, and this constitutes one of the objectives of its use. The permeability of most gravels and coarse sands that are employed in practice is so large compared to that of the sand in place that relatively little loss in production rate will arise from the use of material fine enough to cause the desired resistance to sand migration. For example, in Fig. I is depicted the approximate variation in the permeability of closely sized spherical gravels under the conditions of packing likely to be encountered in screens. The dotted lines indicate the variation that might be found because of differences in packing. It should be realized that the permeability is not a single-valued function of the average grain diameter but is related to a large number of factors, including the size, the size distribution and the shapes of the particles. However, Fig. I does permit a rough estimation of the permeability of closely sized spherical gravels and shows that the permeability with even the smaller particles is very large compared to that of most petroleum production horizons.

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By F. W. Rols-Hausen, F. W. Jessen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By M. C. Leverett

KNOWLEDGE of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum pro-duction, but is as yet incompletely devel-oped. The object of this paper is to show the application of well established thermody-namic and physical principles to these prob-lems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: I. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion of mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. CAPILLARY EQUILIBRIUM IN SANDS Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treat-ment of problems of mixture flow, the con-cepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis-turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predict-able from the theory of capillary equi-librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, of course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is as-sumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reser-voir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems in-volving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately in-vestigated experimentally. Experimental evaluation of the pertinent properties of natural reservoir rocks will permit the ex-tension of the numerical treatment to prob-lems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids; that is, the manner in which the reservoir fluids are distributed vertically when the forces due to capillarity are just balanced by those due to gravitation.

Jan 1, 1940

By F. W. Jessen, F. W. Rols-Hausen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By Stephen Royce

[Stephen Royce.. I .......................... E. S. Moore.. 9 .......................... E. L. Bruce.. 10 ......................... J. E. Hawley.. 11 ........................ L. M. Scofield.. I 2] STEPHEN ROYCE, * Crystal Falls, Mich.Having examined and reported upon the Steep Rock Lake property and vicinity on several occasions for clients, and having kept in touch with the operation from 1938 on, the writer offers the following discussion of the valuable paper by Messrs. Roberts and Bartley, which was so kindly prepared in response to the writer's earnest request, made as a member of the Committee on Mining Geology. ORIGIN OF THE ORES The writer wishes to express complete agreement with the authors that the origin of these deposits was replacement action by hot ascending sulphide solutions of igneous origin, gaining access via the limestone and dolomite breccia channels, and acting mainly to replace the dolomite and limestone breccia with hematite and hydrated hematite. Some replacement in adjoining greenstones and tuffs by the same solutions may also have taken place, but the latter occurrences may represent replaced iron formations originally bedded in with the volcanics. Iron formation in the same relationship to volcanics is extensively developed on the western Menominee Range of Michigan, in the Middle Huronian belts; also appears in similar relations on the Vermilion Range; and is abundantly exposed in the same stratigraphic position no farther away than the southeast arm of Steep Rock Lake itself. Furthermore, the writer's classification of drill cores, made June 11, 1938, on the prop¬erty, contains the following, for hole 8, in the original strike of the A ore body: "332-342 ore; 342-350 much-leached sugary chert with thin ferruginous slate bands." This is a typical iron formation. The ore in this first group of holes (Numbers 6 to 13, incl.) is described in the writer's 1938 notes as follows: "The ore is hard, massive hematite with some limonite, and shot through with many small vugs." The breccia forms in the float ore and in the drill samples were also noted. As a field classification this does not check badly with Professor Schwartz's microscopic work. Notes supplied by Mr. Neeland, then geologist at the exploration, show: "Hole 23 has some iron formation, not logged yet." It appears therefore that there is some iron formation at the exploration, much iron formation in similar stratigraphic position in the vicinity, and iron formation similarly located as to volcanics on the Vermilion and western Menominee Ranges. Certain of the holes, notably Holes 25 and 27, showed some specular hematites resembling those known to be formed from cherty iron formation elsewhere. Hence the writer concludes that at least a small part of the Steep Rock ores results from replacement of iron formation. By far the greater part of it is, as the authors say, clearly a replaced limestone and dolomite breccia, with the breccia outlines still preserved in much of the ore, and all of the replacement is by hot ascending waters. The authors' citation of the neighboring Atikokan pyrite, pyrrhotite and magnetite

Jan 1, 1943

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By Fred W. Stiefel

This paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct. † This part of the tunnel is 15 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 17 to 19 ft. in diameter. It lies at a depth of 400 ft. below sea level, with a maximum overburden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotives, each of 13 gross tons and having a maximum speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 750,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using concrete presented a problem of hading a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 CU. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles. Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. Choice of Locomotives In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. Proposition No. i The 90-hp. storage-battery locomotives the (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1943

By Fred W. Stiefel

This paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct. † This part of the tunnel is 15 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 17 to 19 ft. in diameter. It lies at a depth of 400 ft. below sea level, with a maximum overburden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotives, each of 13 gross tons and having a maximum speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 750,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using concrete presented a problem of hading a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 CU. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles. Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. Choice of Locomotives In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. Proposition No. i The 90-hp. storage-battery locomotives the (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1943

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942