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By John T. Crawford

Much has been written of late regarding the flotation of coal as a means of reclaiming the valuable portion of the fines encountered in nearly all methods of coal preparation. Whether the process be wet or dry, whether the dust be sent through the entire process or removed prior to the cleaning by some such method as screening or aspiration, one of the final products consists of a considerable proportion of — 48-mesh material. The percentage of this —48-mesh material depends upon the mining method, transportation, storage, and method of preparation. The tonnage of this dust material ranges from 1 to 10 per cent of the total output of the cleaning plants. Four methods of disposal are available for this coal: 1. Disposal with the refuse from the plant. 2. Addition, after being reclaimed from the wash water, or dust collectors, without cleaning to the larger sizes. 3. Separate disposal as a pulverized fuel. 4. Cleaning so that addition to the larger sizes benefits the product as a whole. It is also true that flotation in one form or another is the only known way to effectively clean this material. While some processes do a reasonable cleaning job down to and including +l00 mesh, by far the greater majority stop at or short of the + 48-mesh size. Much of the literature on coal flotation passes by the fred pulp density and size by merely stating that the feed varies from 20 to 30 per cent solids and that the size range is from — 1/4 in. or — 1/8 in. to 0. Small wonder then that some operators with entirely different conditions, and not knowing the machine capacity, throw up their hands in despair when flotation is mentioned. Too much parallel is drawn between flotation methods as applied to ores and as applied to coal, to the detriment of the latter. In the flotation of metalliferous ores the feed pulp density ranges from 20 to 30 per cent solids, depending upon the amount of mineral to be floated and upon the size analysis. Thus where 2 to 5 per cent of the

Jan 1, 1936

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of' the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak's theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967

By William Campbell

The structure of iron and steel, though the object of so much study and research for the past 25 years, is by no means thoroughly understood. In the first place, we have three or more distinct iron-carbon thermal diagrams, each with its own supporters, and each representing a theory of the structure and constitution of cast-iron. In the second place, by reason of the fact that austenite, the solid solution of carbon in iron, decomposes in the solid state into ferrite, or pure iron, and cementite (Fe3C), and that quenching from above this transition-range, no matter how rapid, cannot entirely prevent the change and thus preserve the austenite by itself at ordinary temperatures, it happens that under the microscope we find, in addition to the ferrite, Fe3C, and austenite, which the thermal diagram of steel requires, a series of transition-products with distinctive structures, to which have been given the names martensite, troostite, sorbite, etc. Now these transition-products, in addition to the solid solution, austenite, have been the source of much controversy, at times very bitter. One side would insist that, say, troostite was an entity, which the other side would deny, pointing out that it must be a transition-mixture, with a particular structure. That austenite was a solid solution of carbon in iron has been denied by one school; we have been told that Fe24C dissolved both Fe3C and Fe, and thus gave rise to a whole series of quenching-pro-ducts—all this in spite of the fact that no matter how the thermal diagrams differ in regard to cast-iron, they all agree in regard to the solid solution, austenite, for Fe24C finds no place on the diagram. Thus it happens that while the authorities fight both in regard to the iron carbon diagram and the structures met with in hard-

Jan 1, 1913

By G. W. Nabor, M. Mortada

The effects of anisotropic or directional permeability on the areal sweep efficiency and the flow capacity are examined. The paper points out the importance of taking directional permeability into consideration in planning a flood. It analyzes the two-dimensional flow pattern associated with the skewed line drive for a unit mobility ratio. The direct and staggered line drives are treated as special cases of the skewed line drive. Analytical expressions are developed for the areal sweep efficiency at breakthrough and the flow capacity. They are related to the spacing between like wells, the distance between a row of injectors and the nearest row of producers, and the degree of skewness of the line drive. The latter quantity is defined such that it is equal to zero for the direct line drive and equals one-half for the staggered line drive. The areal sweep efficiency and the flow capacity depend also on the orientation of the flood pattern with respect to the principal axis of anisotropy. The paper provides a simple method for determining the areal sweep efficiency and the flow capacity for a formation in which the permeability in the bedding plane is anisotropic. INTRODUCTION Directional or anisotropic permeability is manifested by the ability of the formation to conduct fluids more readily along certain preferred directions. This situation occurs in many producing formationsl-4 and is usually attributed to depositional features in which the sand grains are oriented in a preferred direction. In some cases it results from the formation of a major and a minor fracture system. 4 Directional permeability should be taken into account in many phases of the production and exploration activities. Recognizing its existence in the formation of interest and planning accordingly can lead to increased recovery and substantial savings. For instance, the areal sweep efficiency in a water flood depends to a great extent on the orientation of the flood pattern with respect to the principal axis of permeability. Anisotropic5 permeability is specified by the directions of its three principal axes and the permeability along each axis. The principal axes of permeability are mutually perpendicular. This paper deals with the areal sweep efficiency at breakthrough and the flow capacity for formations with aniscltropic permeability. The flood pattern considered consists of alternate rows of injecting and producing wells. The rows of wells are parallel and form a developed, skewed line drive which is illustrated in Fig. 1. The staggered and direct line drives are treated as special cases of the skewed line drive. PRELLMINARY CONSIDERATIONS The formations considered in this paper are assumed to be of uniform thickness and porosity. The permeability is uniformly anisotropic, with each principal axis of permeability maintaining

By Edward Hart

Having occasion several years since to make ferrous sulphide, I attempted to do so by fusing a mixture of coal-brasses (FeS2) and dried ferrous sulphate. A very nice-looking sulphide was obtained; but on attempting to use it, I found that it was insoluble in dilute hydrochloric and sulphuric acids. The subject was laid aside at the time, but has since been taken up; and some curious results have been obtained, which I believe are new. I have made the material by all of the following methods and the product seems to be pretty much the same, however obtained : (a) FeS2 heated to fusion. (b) FeS2, and FeSO4 heated to fusion. (c) FeS2, and Fe2O3 heated to fusion. (d) FeS2, and FeCO3, heated to fusion. (e) FeSO4, and S heated to fusion. (f) Fe2O3 and S heated to fusion. Obtained in this way the mass after cooling breaks easily and is very nearly black in color. On the upper surface of the fused cake the color is generally reddish or brownish black. When this is treated with dilute sulphuric or hydrochloric acid, it refuses to dissolve; but if touched with the point of a file or any piece of wrought-iron, solution of the sulphide takes place with the evolution of sulphuretted hydrogen. If the iron is removed the evolution of gas ceases, and only begins again when the iron is again brought into contact with the fused sulphide. The same thing happens if the iron is connected with the sulphide by means of a platinum wire. But in all the samples of fused sulphide I have obtained, if the iron is allowed to remain in contact with the sulphide for a certain time (which varies with different samples of the fused sulphide) and is then removed, solution of the sulphide continues. Zinc, tin, and magnesium have the same effect as iron. In hydrochloric acid aluminium acts more rapidly even than iron. In sulphuric acid it has little if any effect. Copper in HCl, when brought in contact with the fused sulphide, dissolves quietly without evolution of gas. The solution of copper chloride formed becomes,as it flows down over the sulphide, converted into copper sulphide.

Jan 1, 1887

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.' Approximate analytical solutions' were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.' A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg' gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case'" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

Prof. Henry M. Howe, New York, N. Y. (communication to the Secretary*):—The results presented in Mr. Mathewson's paper are of very great interest. Perhaps the most interesting is that shown in Table I. and Fig. 1, in which the arsenic decreases in 10 min. from 0.22 to 0.07 per cent. This is such a large decrease that it is to be hoped that Mr. Mathewson will verify it by repeating his tests with a matte of similar composition. This is particularly to be desired, because the simultaneous removal of sulphur appears to be very small. All three blows further agree in showing that the removal of arsenic is in the very early part of the blow. The fact that the removal of arsenic then ceases abruptly cannot be explained completely by the fact that the arsenic has fallen so low as by its lowness to resist further removal, because in the first blow the arsenic becomes stationary at 0.06 per cent., whereas in the third blow it does not become stationary until it has fallen to 0.034 per cent. The abrupt ending of the removal of arsenic is more likely to find its explanation in the composition of the slag, and it is to be hoped that Mr. Mathewson will supplement these extremely valuable data with others in which the composition of the slag at the same time shall be given. The sudden rise of arsenic toward the end of the third blow I suppose must be referred to an error in sampling or analysis.

Jan 1, 1908

By B. W. Dyer

In 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KCl) and carnallite (KMgC12.6H2O). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. Location and Geology of Deposits The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado River— a distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 20 E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 20 E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 1/2 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel

Jan 1, 1948

By B. W. Dyer

In 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KCl) and carnallite (KMgC12.6H2O). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. Location and Geology of Deposits The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado River— a distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 20 E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 20 E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 1/2 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel

Jan 1, 1948

By Joseph E. Pogue

The outstanding features of 1926 in the petroleum industry included the following: 1. Stocks of all oils (crude and refined) were reduced, making the first annual decline since 1918. 2. Domestic crude oil production increased steadily during the last 11 months of the year, accelerating during the fourth quarter, and ending the year at the highest level ever attained. 3. Three new major oil fields were developed—Panhandle, Spindle-top and Seminole. 4. Important advances were registered in production technique, tending to retard the declines of old wells and to maintain the flush periods of new wells. 5. The problem of gaining greater economic control of production through unit operations and gas conservation received growing recognition by the industry and the Federal Oil Conservation Board. 6. The rate of drilling was sharply increased during the second quarter of the year and suffered only a very slight retardation during the closing months. 7. The runs of crude oil to stills were maintained above normal throughout the year and underwent acceleration during the fourth quarter. 8. The gasoline situation was marked by a continuous and substantial increase in the rate of production of cracked gasoline, and by an improvement in the statistical position of the commodity. 9. Prices of both crude petroleum and its principal derivatives were characterized by more profitable levels and greater stability than for a number of years past; and, while showing declines during the fourth quarter, prices did not recede sufficiently to slow down materially either drilling or refinery operations. Change in Stocks The keynote of 1926 was a reduction in stocks of all oils to the extent of approximately 24,000,000 bbl., or 4.4 per cent., of which roundly

Jan 1, 1927

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By Plato Malozemoff, A. M. Gaudin

IN modern practice the major portion of an ore is reduced to flotation size by fine grinding. As the result of grinding fine enough to liberate most of the minerals, a substantial portion (generally 5 to 15 per cent) of the ore is inadvertently reduced to a size much finer than that necessary for liberation. This portion of most flotation pulps is very refractory to recovery by flotation. A reduction of one-quarter or more in recovery in this range of extremely fine particles can be observed. The loss in metals caused by overgrinding is appreciable. That this loss is characteristic of very fine particles has been suspected for some time;(l)† however, it was definitely quantified only recently.(2) Definite reduction in float-ability with reduction in particle size beyond a critical size of maximum floatability can be accepted now as an established fact. Formulating the Hypothesis In looking for the cause of the ill behavior of the finest particles it may be well to consider the essential differences between fine and coarse particles. A difference that immediately comes to mind is their intrinsic difference in size and consequently in relative extent of surface. If one agrees that attachment of mineral particles to bubbles must follow direct encounter of particles with bubbles one is forced to conclude(3) that the probability of encounter between a mineral particle and a bubble varies directly as the size of the particle, provided the particle is small compared to the bubble. In other words, the finer the particle the poorer its chance of being recovered in a given time of flotation. There is an effect, implicit in this theory, which should overcome the effect of excessive fineness of the particles; namely, flocculation of the particles. The floccules can be conceived as being simply larger particles and therefore capable of becoming attached to bubbles. And, indeed, in all the cases in which a sulfide mineral of near-colloidal size was successfully floated the mineral (but not necessarily the gangue) was flocculated. Moreover, it was shown experimentally(4) that galena previously flocculated by inorganic flocculators and then added to gangue

Jan 1, 1935

By H. S. Jerabek, Charles S. Barrett, Robert F. Mehl

The precipitation of the nitride Fe4N from the solid solution of nitrogen in a Fe and of the phosphide Fe3P from the solid solution of phosphorus in a Fe both lead to the formation of structures that may be easily identified as Widmanstatten figures, within the meaning of the term as used in this series of papers. A complete solution has been obtained for the figure formed by Fe4N. The structure of Fe3P, however, is not fully known and a complete solution of this figure thus cannot be obtained; nevertheless, a study of this figure has furnished some new information. Precipitation of Fe4N from Alpha Solid Solution of N in Alpha Fe Constitution of System Iron-nitrogen A knowledge of the constitution of the whole of the Fe-N system is unnecessary for this work, though the recent studies by Eisenhut and Kauppl and by Lehrerz have clarified most of the moot points; it is sufficient for our purpose to state that a Fe of high purity dissolves 0.42 per cent of nitrogen in solid solution at the eutectoid temperature, 591' C., and that this solubility decreases at first rapidly and then more slowly until at room temperature the solid solubility amounts to approximately 0.1 per cent nitrogen.3

Jan 1, 1934

By E. Teghtsoonian, A. R. Causey

THE fact that the surface plays an important role in the plastic deformation of a single crystal has been demonstrated by several investigators. The surface conditions have been altered using oxide films,1'2 alloyed metal layers,3, 4 deposited metal films,' and polycrystalline layers.677° The resulting effects on the initiation and subsequent plastic deformation have been investigated extensively except for the case of a single crystal surrounded by a polycrystalline layer of the same material. The purpose of this paper is to describe an investigation of the effect of a polycrystalline surface layer on the yield stress, the critical resolved shear stress, and the work-hardening slope of tin single crystals. The tin single crystals used in this study were grown from the melt using material having an initial purity of approximately 99.999 + pet with lead and iron the major impurities. Fig. 1 shows the orientation of the (110)[001] slip system with respect to the crystal surfaces. The crystals had a 1/4 by 1/4 in. cross section and a gage length of 2 in. The polycrystalline surface layer was produced by abrading the single-crystal specimens with emery paper. Fig. 2 shows the broken Debye rings obtained from the deformed surface. The thickness of the layer was controlled by the number of passes on different grades of paper and was determined by electropolishing in dilute HC1, until the grains produced by the abrasion had all been removed. Metal-lographic examination showed that the grain size varied with depth, increasing from 10 µ right at the surface to 40 µ in the interior of the layer. The yield stress, critical resolved shear stress,

Jan 1, 1965

By Persifor Frazer

I DESIRE to say that, owing to the number of papers which have been more or less crowded at this session of the Institute, and the fact that, as one of the Local Committee, I have the distinguished honor to feel somewhat like one of the hosts, I should not tax the patience of members at this late hour, but would have my paper read by title were it in any way possible to do this. But the task I have set myself this evening is to present to the eyes of the members of the Institute certain objects which have occupied more or less of my time during the last eighteen months or two years. The objects I allude to are some of the igneous rocks of this country, which, until quite recently, have been less understood than any others. It will be well known to some of the members that some of the cooled lavas of a previous age of our planet, when not directly coarsely crystalline and granular, were considered and spoken of as " natural glasses," or perfectly uncrystalline, vitreous, or hyaline masses of matter. Among the first results of the use of the microscope was the dispersion of this fallacy. Sir David Brewster, Mr. H. C. Sorby, and William Nichol (the discoverer of the celebrated calcite prism, which bears his name), had, with greater or less success, examined sections of various rocks and minerals, both by transmitted and reflected light, and also in the form of powder. But, until the genius of Vogelsang undertook the subject, these investigations had no permanent value, nor did they constitute an independent line of mineralogical and geological research. Since the close of his labors, by Vogelgang's premature and much-lamented death, the subject has been made one of renewed interest by his brother-in-law, Ferdinand Zirkel, as well as by Rosenbusch, Tschermak, and many others abroad, and at home by the commencement of a systematic study of the traps of Connecticut by Messrs. E. D. Dana and G. W. Hawes, of New Haven, and by the splendid set of described sections of the traps of the West which have been furnished by Zirkel to illustrate Clarence King's report. I had the honor of presenting a large number of thin sections of our traps at the Washington meeting, for the inspection of the mem¬bers, with the aid of a table microscope belonging to the Smithsonian Institution. Here I propose to project these sections upon the

Jan 1, 1877

By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963

By Wallace W. Wilson

The Cook Ranch Field produces from a very permeable lens of Cook Sand of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The field was discovered in 1926, and has been operated with low pressure gas injection since July, 1927, one of the first such projects in Texas. Cumulative recovery to Dec. 31. 1950, was 14,701,131 bbl of crude oil, an average of 1,013 bbl per acre-ft of oil rection. and 72.5 per cent of the oil originally in place. Analysis of the reservoir performance indicates that grav-ity drainage has been an important factor in the producing mechanism. The high permeability and uniformity of the reservoir were extremely Favorable tor this type of operation. INTRODUCTION The Cook Ranch Field is the largest of a number of relatively small, shallow producing areas near .Albany, in Shackelford County, Texas. This field is one of the first to be operated by gas injection in Texas, and probably is the most successful low pressure gas injection project ever attempted. The field is owned entirely by Koeser and Pendleton, Inc., and Continental Oil Co., and has been operated by Roeser and Pendleton, Inc., since it was discovered. This study has been made possible through the cooperation of Roeser and Pendleton, Inc.. in making availahle a remarkably complete set of records covering all phases of their operations. The purpose of this paper is to present a summary of the history of the operations through Dec. 31, 1950, and to analyze some of the factors which appear to be responsible for the success of the project. Information concerning the physical plant and the early gas injection history has been presented in an earlier paper.' RESERVOIR CHARACTERISTICS production in the Cook Ranch Field is from a large lens of Cook Sand. of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The average dip of the sand body, as shown in Fig. 1. is only about 50 ft per mile to the northwest. The reservoir has an area of 930 acres and contains 15,512 acre-ft of Sand, consisting of about 14.512 acre-ft of produc-tive oil zone. and an estimated 1.000 acre-ft of primary gas-cap. The iso-pachous map (Fig. 2) was prepared from drillers' logs. Recent coring in the field has proven these logs to be quite accurate. The productive limits of the field are defined by shale on all sides but the southwest where a small zone of edgewater was encountered. This water does not appear to have encroached into the reservoir, and water production has been small. A smaller producing area to the south of the Cook Ranch Field also produces from the Cook Sand. but is separated from the reservoir under consideration by a band of shale. The sand consists of well sorted, coarse grained. rounded and subangu-lar quartz fragments. very poorly cemented. The analysis of 46 chip-core samples from two recently completed test wells indicates a range of porosity values between 12.5 and 28.2 per cent. wit11 an arithmetic average of 24.0 per cent. Air permeability values range between 50 and 2,300 md, with an arithmetic average of 1.200 md. The reservoir where cored is a Solid sand body. with no discernible major shale breaks or impermeable streaks. Vertical permeability appears to be of the same magnitude as the horizontal permeability. A core of the Cook Sand was cut ill the smaller field to the south, using lubricating oil as drilling fluid. The connate water content of the sand in this core was found to average about ten per cent, and the porosity and permeability were comparable with the values reported above. No analysis was made of subsurface or recombined hydrocarbon samples,

Jan 1, 1952

By K. V. S. Sastry

This paper summarizes recent research on the kinetic aspects and process behavior of agglomeration in balling circuits. The physical concepts underlying agglomeration, the mechanisms responsible for size changes during agglomeration, and a generalized population balance model for agglomeration systems are summarized. Experimental techniques for investigating the batch balling behavior and for simulating the balling- circuit operations are reviewed. Further, the effect of such operating variables as feed moisture, bentonite content, and the rate of feed addition are discussed. An approach to the computer simulation of the agglomerating circuits is shown and the importance of such models in process engineering is discussed.

Jan 1, 1977