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By Joseph B. Umpleby

WHEN the Cushing field flooded the oil market in 1914 and 1915 with a daily output equal to nearly one-third of the world's production, the situation was soon corrected by increased consumption, and the price of crude oil rose from 45 c. per barrel in, February 1915 to $1.10 in December of the same year-the highest price paid in the Mid-Continent field up to that time. The intensive search for oil during the following seven years failed to disclose a single new ,field equal to Cushing, and many observers concluded that the rapidly increasing number of wells contributing to the world's output, each declining roughly 20 per cent. a year, combined with the rapidly increasing con¬sumption of petroleum, made it highly improbable that any field would; be found again sufficiently large to seri¬ously affect the oil market. That seven exceptional fields should then be discovered simultaneously is a remarkable coincidence. Long Beach, Santa Fe Springs, and Powell, each exceeded Cushing in daily output and reached the apex of their production during a year when Burbank, Tonkawa, - Smackover and Huntington Beach each contributed several times the daily output of the average new pool. This unexpected and tremendous flood of flush production could only have the effect of depressing price and greatly adding to stocks throughout the country. It was particularly depressing in the Mid-Continent as the new oil from California proved of attractive refining grade and because of cheap transportation by water easily undersold Oklahoma crude in the eastern markets.

Jan 1, 1924

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800' and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,',' in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.' , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961

W. L. Saunders, New York, N. Y. (communication to the Secretary*):—The Laramie tunnel, though a small one, compares very favorably in the speed of driving with the great Alpine tunnels which have the record so far. I think it safe to say that, taking all things into consideration, the record made at Laramie is the best American record, though it still falls short of the long-tunnel records abroad. In discussing tunnel-records it must always be borne in mind that there are conditions peculiar to each individual tunnel job, so that no comparisons are complete, fair and conclusive. At Laramie there is one point which stands out prominently, and which distinguishes this from any of the recently-built Alpine tunnels, and that is that here we have great progress in an American driven tunnel without the use of a carriage for mounting the drills. At the Arlberg and Loetschberg tunnels, the carriage was an essential condition for progress. All the heading-drills were mounted upon a bar which rested upon a small carriage. This carriage was withdrawn after the drilling and run into the heading after the blast without much disturbance of the drills, and with very little adjustment except that required in jacking the horizontal bar across the tunnel. The carriage was so small in its track-area that it required little mucking to run it in to the face; and as the rock-drills used were heavy machines 38 in. in diameter, progress in setting up and drilling was very much accelerated by the use of the carriage. At the Laramie tunnel hammer-drills were used instead of piston-drills, and here we have an important distinction which

Jan 1, 1913

By M. C. Leverett, W. B. Lewis

The dynamic behavior of a multiple fluid system is completely describable in terms of driving forces and resistances to flow. The latter are proportional to the viscosity of the fluid under consideration and inversely proportional to a property of the system termed the " effective permeability " to that fluid, a property therefore defined by this relation. Since three phases are usually present in oil reservoirs, it is essential to know the effective permeabilities to the several fluid phases, and the relationship between the composition of the fluid in the pore space and that of the flowing stream, in order to handle satisfactorily certain problems of oil production. In this regard, there are many unknown factors and parameters, and many that can be evaluated only indirectly. However, it is expected that work along lines similar to this present undertaking will help materially in solving these problems. .. . . Previous workers in this field have investigated the two-phase systems, water-gas,' water-oil2 in unconsolidated sands, and water-gasg in consolidated sands. The extension of the study of the flow of heterogeneous fluid systems from two to three phases involved only slight changes in technique. The apparatus used in the present work, except for slight changes to be described, was that used by Leverett in his water-oil experiments.~ Correlation and interpretation of data were made by methods analogous to those used in two- phase work. The relative permeability to a phase—the effective permeability divided by the permeability of the system to a homogeneous fluid—was employed throughout in correlating the rate of flow of that phase with the composition of the pore space. Quantitative measurements of two independent physical properties of the system were required to determine the composition of the pore space. As in the two-phase work, the fraction of water was determined electrically, The gas fraction was determined by measuring changes in volume accompanying measured pressure changes. Suitable account was taken of the solubility of the gas in the liquid phases, and of the vapor pressure of the water phase. Since this work was exploratory in nature, no attempt was made to obtain highly accurate numerical results. Reasonable precision and reproducibility were sought. Experimental Procedure variables Considered.—Of the properties of the fluids, the oil viscosity is most likely in practice to vary widely. Variations in oil viscosity were therefore included in this work, but variations in other properties of the fluids are as yet unexplored. It appears unlikely that the normally encountered variations will produce significant changes. ~h~ observations were made at fairly high pressure gradients, no attempt being made to detect a variation of the relative permeabilities with pressure gradient. It should be pointed out also that since most of the data were taken on one sand size only, it call Only be assumed at present that changes in

Jan 1, 1941

By W. B. Lewis, M. C. Leverett

The dynamic behavior of a multiple fluid system is completely describable in terms of driving forces and resistances to flow. The latter are proportional to the viscosity of the fluid under consideration and inversely proportional to a property of the system termed the " effective permeability " to that fluid, a property therefore defined by this relation. Since three phases are usually present in oil reservoirs, it is essential to know the effective permeabilities to the several fluid phases, and the relationship between the composition of the fluid in the pore space and that of the flowing stream, in order to handle satisfactorily certain problems of oil production. In this regard, there are many unknown factors and parameters, and many that can be evaluated only indirectly. However, it is expected that work along lines similar to this present undertaking will help materially in solving these problems. .. . . Previous workers in this field have investigated the two-phase systems, water-gas,' water-oil2 in unconsolidated sands, and water-gasg in consolidated sands. The extension of the study of the flow of heterogeneous fluid systems from two to three phases involved only slight changes in technique. The apparatus used in the present work, except for slight changes to be described, was that used by Leverett in his water-oil experiments.~ Correlation and interpretation of data were made by methods analogous to those used in two- phase work. The relative permeability to a phase—the effective permeability divided by the permeability of the system to a homogeneous fluid—was employed throughout in correlating the rate of flow of that phase with the composition of the pore space. Quantitative measurements of two independent physical properties of the system were required to determine the composition of the pore space. As in the two-phase work, the fraction of water was determined electrically, The gas fraction was determined by measuring changes in volume accompanying measured pressure changes. Suitable account was taken of the solubility of the gas in the liquid phases, and of the vapor pressure of the water phase. Since this work was exploratory in nature, no attempt was made to obtain highly accurate numerical results. Reasonable precision and reproducibility were sought. Experimental Procedure variables Considered.—Of the properties of the fluids, the oil viscosity is most likely in practice to vary widely. Variations in oil viscosity were therefore included in this work, but variations in other properties of the fluids are as yet unexplored. It appears unlikely that the normally encountered variations will produce significant changes. ~h~ observations were made at fairly high pressure gradients, no attempt being made to detect a variation of the relative permeabilities with pressure gradient. It should be pointed out also that since most of the data were taken on one sand size only, it call Only be assumed at present that changes in

Jan 1, 1941

By Eugene Leonardon

THE search for oil has required, and without a doubt supplies, a tremendous amount of information on the structure, composition, physical properties, and history of sedimentary rocks. The earliest and most complete source of knowledge is the sample or core of the rock itself, the uses of which are well known. The purpose of this paper is primarily to discuss a new method for obtaining these cores, and to illustrate its use in connection with electrical logs. Most cores have been obtained through a special adaptation of rotary drilling, and the results have been remarkably good, considering the mechanical problems involved. Unfortunately, because of the time and expense, this method cannot be used for the entire length of the drill hole. Even though ingenious contrivances have been evolved in order to reduce the time spent in round trips, such as wire-line coring equipment, mechanical coring still remains too expensive to be carried out con-tinuously. In practice, therefore, one is finally compelled to estimate the probable depths of the more interesting horizons and, allowing a wide margin of safety, to core through those sections only. It is true also that interesting results have been obtained by examining the cuttings brought to the surface by the mud circulated in the well during the process of drilling. Be that as it may, the inescapable fact remains that key horizons may be passed inadvertently, for one reason or another, while the drilling operations are being performed. The only continuous record of the formations encountered is that furnished by electrical surveys. Obviously, it would be desirable to make the electrical survey first and to take the samples from the wall of the hole according to the indications on the electrical log. In this way, it would be possible to core only the exact sections desired, eliminating the otherwise inevitable estimates as to the point at which to start coring, and thereby reducing to a minimum this expensive operation. At the same time this method would provide a maximum' of useful samples.

Jan 1, 1939

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By Louis A. Carapella, William E. Shaw

MAGNESIUM and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitional point has been set at 225°C by Schmid1 for single crystals, and at 250°°C by Morell and Hanawalt2 for extruded magnesium metal. In a recent X-ray investigation on polycrystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional temperature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheett over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig r. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Hargreaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Hargreaves constant S, was obtained by the integrated or intermittent loading procedure. The authors5 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformational loads. These findings have been applied

Jan 1, 1947

By J. E. Johnson

It is the purpose of the present paper, while not excluding chemical considerations, to deal more extensively with some of the physical and mechanical aspects of the blast-furnace process, and to point out its dependence, in these respects, on well-known laws. The quantity and cost of ore and flux required to make a ton of iron being determined by circumstances over which the furnace-man, under given conditions as to quality and quantity of product, has commonly little control, the principal item of cost, apart from the saving of labor, which he can aspire to reduce, is that of fuel. To determine the limits of possibility in this direction is clearly the first step in a practical inquiry; and this step is represented herewith in Fig. 1, a diagram showing the total useful effect obtained from a pound of fuel under various conditions, and thus permitting direct comparison, under any given conditions, between actual results and the maximum possible results. The following statements will explain the basis upon which this diagram has been constructed. One pound of fuel, containing 90 per cent. of fixed carbon (which represents average conditions), is taken as the unit. The degree of oxidation of the carbon is measured by the ratio of the two oxides of carbon contained in the top-gases. It is necessary to remember that a considerable quantity of carbon is brought in as carbon dioxide by the flux, and to take account of it and of its condition. It is here considered that the carbon dioxide liberated by the limestone does not affect the analysis of the top-gases, and that the ratio of CO to CO2 will remain unchanged by the addition of limestone; enough CO, being reduced by the solution

Jan 1, 1906

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

The negative charges on diaphragms of quartz, tungstic oxides, stannic acid, acid dyestuffs, soaps, and glass have for a number of years been explained on the basis of chemical equilibria—a hydrogen ion or light metal ion passes into solution leaving the solid complex ion negatively charged. While there are a number of observations which indicate a proportionality between the ( potential and the streaming potential it should be recognized that all the experimental evidence thus far presented shows that if hydrogen ion concentration is kept at a constant value, electrokinetic phenomena are influenced by salts. The multivalent ions exert the greatest effect on the reduction of osmotic flow. In the interpretation of all electrokinetic data the assumption is made that the potential of the solid remains constant. That this is not true is evidenced by the values of [ potential for quartz in contact with conductivity water as reported by the several investigators and by the authors of this paper. It is apparent that the nonreproducibility of surfaces will always prevent the obtaining of exactly comparable data. At best the experimental technique described depends on a theory which is capable only of showing a trend—another quartz surface should exhibit similar but not identical potential curves. It seems entirely reasonable to assume that the negatively charged laurate ions should have little or no attraction for a negatively charged quartz surface. The weight of previous experience in selection of flotation activators points unerringly to the usefulness of the multivalent metallic ions. The primary reason why the divalent barium ion is not available to two negative charges on the quartz surface might easily be that of distance between such adjacent negative charges. Otherwise activation could not occur, and the quartz could not assume the remaining unit positive charge of the barium ion. For this case no electrical double layer theory seems necessary. Clearly this is, at the negatively charged quartz surface, a case of partial chemisorption of the cationically divalent barium ion followed by the anionic neutralization of the remaining cationic charge by the freely moving laurate ion. It is hoped that the authors will continue with this interesting technique and that their results will continue to indicate trendwise what is known about the

Jan 1, 1957

By O. G. Bell

While all of the Southwest Texas fields lie within the Gulf Coastal Plain this area may be divided into three subdivisions—the Coastal Plain zone proper, the Reynosa Escarpment zone, and the interior zone. The Coastal zone includes that strip adjacent to the Gulf of Mexico and . extending inland for a distance of about 60 miles and includes the Palo Blanco, Palangana, Piedras Pintas, Kingsville, Agua Dulce, Saxet, White Point and Refugio fields. The Reynosa Escarpment zone includes a Pliocene overlap over older Tertiary sediments lying west of the Coastal zone. The western margin of the Reynosa formation forms a more or less well-defined westward facing escarpment with which the so-called Reynosa Escarpment fields are indirectly related. These fields include those in eastern Zapata, eastern Webb, western Jim Hogg, western Duval, McMullen, Live Oak, Bee, Goliad and Victoria counties. The interior zone includes these fields west of the Reynosa Escarpment which are not in any way related to it and are on separate types of structure. Production data by fields and wells are shown in Table 1. Roma.—During 1928 the Texas Co. completed two small gas wells at 198 ft. on the Roma Structure near the town of Roma on the Rio Grande in Starr County. This gas is of no commercial importance but was used for fuel in drilling other deep tests on this structure. Three dry holes ranging from 3600 to 4200 ft. were drilled; then their No. 4 Guerra, the fourth deep test, was completed during December as a small producer of 37" Bé. oil from a sand at 3560 to 3590 ft. No production was marketed during December but arrangements were being made to handle the output from this well during 1930. This is the first commercial producer in Starr County. Driscoll.—In 1929, Robert Driscoll discovered gas on his Santa Rosalia Ranch in Duval County while drilling water wells. Two sands were developed, one at 2400 ft. and another at 2936 ft. and several gas wells were completed in each, ranging in volume from 15,000,000 to 40,000,000 cu. ft. and in reservoir pressure from 500 to 1,000 Ib. Early in January of 1929, Mr. Driscoll's No. 14 Fee was completed as a 50-bbl. oil producer at 2894 ft. Two other oil producers were completed early in 1929. Mr. Driscoll's death early in the year curtailed develop-

Jan 1, 1930

By Norman P. Goss

What would appear to be a very simple process on paper has proved to be overrun with a multitude of unseen difficulties. For more than 70 years attempts have been made to cast metals in a continuous manner, but it has been only within the last Io years that some degree of success has been achieved.1 Historical Development Bessemer's Experiments—Method I Bessemer was the first to try to cast molten metal in a continuous manner. His method is fully described in U. S. Patent No. 49053, issued in 1865. The patent drawing is shown in Fig. I. In this method the molten metal was poured between a pair of rolls of large diameter, which were cooled by water sprays. Means were provided to prevent moisture from coming into direct coptact with the molten metal. The width of the strip was controlled by the flanges. On paper this should work to perfection, but it is beset with many difficulties still awaiting solution. Bessemer failed to reduce his invention to commercial practice. About 1890 Bessemer's method was revived by Norton and associates (U. S. Patent No. 441375). They formed the Fluid Metal Rolling Co. at Maywood, Ill., and spent $250,000 in endeavoring to develop the technique for this simple method. Finally they had to abandon it. Naturally, they did carry the technical development far beyond anything Bessemer had done, but even so it was far from being a useful commercial success. In recent years it has undergone further development by C. W. Hazelett (U. S. Patent No. 2058447), who has succeeded in obtaining long lengths of copper, brass, aluminum, and even stainless steel. He introduced many' ingenious devices but the greatest obstacle still remained—the disintegration of the roll surface when the surface is heated and chilled in rapid succession. Difficulty is also experienced in maintaining a uniform supply of molten metal to the rolls. The patents pertaining to this method would indicate these to be the major obstacles. Experimental work by Mellen—Method 2 A departure from the method introduced by Bessemer, was tried by Grenville Mellen, of East Orange, K. J., sometime between 1914 and 1920, who obtained a number of patents.2 His method is illustrated in Fig. 2. This method failed to make an impression upon the art; however, it is of value in pointing out the difficulties the inventor ran into and the way in which he tried to meet them. The split mold sections form two endless chains. When going through the center of the apparatus, these sections engage each other to form a complete mold. As the engaged mold section moves downward at a constant speed, molten metal is teemed into it. As this is going on, another set of cooperating mold sections move into position on top of the one being filled. The molten metal is teemed into the mold through a silica tube. According to the teachings of this patent, the level of molten

Jan 1, 1945

By J. H. Brophy

Experimental evidence in recent years shows that nickel coated hydrogen reduced tungsten powder can be sintered to 98 pct of theoretical density at 1100°C. New data indicate that the sintering rate is the same for nickel contents ranging from 0.125 wt pct (mon-atomic layer) to 5.0 wt pct Ni coated on 0.561. tungsten powder. Nickel tungsten made by coreduction from oxides sinters in a kinetically similar way, but the rate tends to increase with higher nickel contents. The activation of sintering can be accomplished with a minimum amount of nickel if coated powder is used. Transverse rmpture strength was found to increase in specimens containing 0.25 pct Ni as density increased during the initial stage of the carrier-phase sintering process. Upon the onset of grain growth in the final stage, strength was found to decrease. With increasing nickel contents up to 4 pct, strength increased. Maximum strengths in three-point loading were observed at 73,000 psi for 0.25 pct Ni and 93,000 psi for 5 pct Ni. These were comparable to that of massive tungsten recrystal-lized in the presence of nickel and tested in the same way. The results were sensitive to the mode of powder treatment and ductility was negligible in all cases. The study and application of sintered bodies of nickel and tungsten is not new; however, the analysis of the mechanism by which small additions of nickel increase the sintering rate of tungsten promises to Contribute new information regarding sintering theory in general. Initial experimental evidence was presented by the authors showing that nickel-coated hydrogen-reduced tungsten powder may be sintered to 98 pct of theoretical density at 1100°C in 16 hr.' Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the 'solution-precipitationo step postulated when the carrier phase is liquid3 although in the nickel tungsten case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in mi-crostructures at the temperatures under consideration. In the present work, new data for nickel-coated tungsten powder are offered in support of the proposed mechanism, and a more explicit study of the second stage of densification is presented. Concurrently, the sintering kinetics of these coated powders are compared to Ni-W powder made by coreduction of oxides. In this way the present work can be compared to earlier results in nickel activated sintering of tungsten in which the coreduction process was emplyed. The ultimate utility of such an activated sintering process will be determined to some extent by the mechanical and physical properties of the final prod-

Jan 1, 1962

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By H. J. Hager, P. H. Haskell

For the past 20 years Alabama has probably led all other coal-producing districts in the proportion of coal prepared by wet washing. All rail mines, with one exception, and a high percentage of truck mines now wash all coal under 3 or 4 in. Most of this coal has been cleaned by jigs, though within the past few years one or more wet-table plants have been installed for cleaning some of the coal from practically all the major seams. These tables supplement either single or multicell jigs usually for one of the following purposes: (I) to wash the finer sizes of raw coal, (2) to rewash the finer sizes of washed coal after they leave the jigs, (3) to re-treat jig middling products. The main purpose of this paper is to present cleaning data and operating factors involved in the preparation by tables of the finer sizes of raw coal. The specific information and data pertain to the Mary Lee seam of coal as extracted at three of the mines of the Alabama By-Products Corporation, which produces coal for both byproduct coke-oven consumption and the general steam market. The Mary Lee seam has long been recognized by coal-preparation authorities as presenting a very difficult ash-reduction problem. Washing characteristics and physical structure of the seam vary widely. Its thickness ranges from 32 in. with no rock parting to 100 in. with from one to three partings. Over the entire field the bed contains bands of bone and rash. These are distributed throughout the seam cross section. A portion of this bone or bony coal occurs as definite bands I in. or more thick; however, some bone is interlocked as layers within the coal and consequently breaks into flakes when the coal is broken. This material is relatively high in ash and its specific gravity varies widely. It has been observed that in most cases in the washing of Mary Lee coal from 10 to 18 per cent of the raw coal is within +0.10 specific gravity of the attempted point of separation. Therefore with the average wet jig, only with extreme difficulty can a low-ash product be obtained without loss of much marketable coal in the refuse. Without entering into the controversial question as to whether modern washing equipment can efficiently handle simultaneously all sizes up to a given maximum, suffice it to state that the comparatively old-type jigs in service at the Alabama By-Products Corporation's mines could not clean the he sizes satisfactorily. Therefore, in 1931 that company installed six diagonal-deck tables at the Barney mine, which were installed as an addition to a complete plant cleaning all coal below minus 3 in. The primary washed product is shipped as steam coal and another portion may be prepared as washed nut for domestic trade. These tables are washing 9 tons per hour of raw coal sized to ¼ in. to o. The washed table coal is mixed with the 3 to ¼-in. jig product to constitute a 3 in. to o steam coal.

Jan 1, 1942

By H. J. Hager, P. H. Haskell

For the past 20 years Alabama has probably led all other coal-producing districts in the proportion of coal prepared by wet washing. All rail mines, with one exception, and a high percentage of truck mines now wash all coal under 3 or 4 in. Most of this coal has been cleaned by jigs, though within the past few years one or more wet-table plants have been installed for cleaning some of the coal from practically all the major seams. These tables supplement either single or multicell jigs usually for one of the following purposes: (I) to wash the finer sizes of raw coal, (2) to rewash the finer sizes of washed coal after they leave the jigs, (3) to re-treat jig middling products. The main purpose of this paper is to present cleaning data and operating factors involved in the preparation by tables of the finer sizes of raw coal. The specific information and data pertain to the Mary Lee seam of coal as extracted at three of the mines of the Alabama By-Products Corporation, which produces coal for both byproduct coke-oven consumption and the general steam market. The Mary Lee seam has long been recognized by coal-preparation authorities as presenting a very difficult ash-reduction problem. Washing characteristics and physical structure of the seam vary widely. Its thickness ranges from 32 in. with no rock parting to 100 in. with from one to three partings. Over the entire field the bed contains bands of bone and rash. These are distributed throughout the seam cross section. A portion of this bone or bony coal occurs as definite bands I in. or more thick; however, some bone is interlocked as layers within the coal and consequently breaks into flakes when the coal is broken. This material is relatively high in ash and its specific gravity varies widely. It has been observed that in most cases in the washing of Mary Lee coal from 10 to 18 per cent of the raw coal is within +0.10 specific gravity of the attempted point of separation. Therefore with the average wet jig, only with extreme difficulty can a low-ash product be obtained without loss of much marketable coal in the refuse. Without entering into the controversial question as to whether modern washing equipment can efficiently handle simultaneously all sizes up to a given maximum, suffice it to state that the comparatively old-type jigs in service at the Alabama By-Products Corporation's mines could not clean the he sizes satisfactorily. Therefore, in 1931 that company installed six diagonal-deck tables at the Barney mine, which were installed as an addition to a complete plant cleaning all coal below minus 3 in. The primary washed product is shipped as steam coal and another portion may be prepared as washed nut for domestic trade. These tables are washing 9 tons per hour of raw coal sized to ¼ in. to o. The washed table coal is mixed with the 3 to ¼-in. jig product to constitute a 3 in. to o steam coal.

Jan 1, 1942