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By H. H. Rachford

Numerical solutions of immiscible flow problems in which dispersive effects of capillarity are dominated by convection require excessively fine grid spacing with attendant high computing costs. The use of coarser spacing reduces cost but often produces oscillation or undue dispersion associated with displacement fronts, A numerical formulation is proposed here which should be applicable to two-dimensional flow problems. it is in part analogous to an approach previously tested for miscible systems. The convective transport is approximated using a change of variables to yield a coordinate system moving approximately with the local characteristic velocity. The capillarity-induced dispersive terms in the differential system describing the process are approximated with respect to a fixed coordinate system by the usual implicit formulation. One-dimensional tests of the procedure yielded results in which the saturation profiles tended smoothly to the zero-capillary pressure solution as the ratio of viscous to capillary forces was successively increased in a sequence of calculations. This contrasted favorably with solutions by other numerical procedures which would require attendant grid refinements to approach the zero capillary pressure results. INTRODUCTION Numerical solution of displacement problems has until recently relied on applying methods developed primarily for transient heat-flow problems. Such problems are classified as parabolic in type, and where the heat transport is purely by diffusion their solutions are characterized by a high degree of smoothness. It is not surprising, therefore, that for approximating these solutions available finite difference methods are quite adequate. In flow problems the transport is partly by diffusion, partly by convection or flow. Although the problem remains of parabolic type because the dispersive effects of capillary forces or diffusion play some role in every displacement, at high flow rates the problem is dominated by convection, and solutions tend toward those of equations of the hyperbolic type. Solutions of hyperbolic problems are characterized by the translation of fronts, or discontinuities, that may progressively increase in sharpness. Numerical methods for treating parabolic problems become less and less satisfactory as displacement rates increase and the role of dispersion due to concentration or capillary pressure gradients becomes small relative to transport due to flow. In computation the difficulty manifests itself as an error associated with the grid size chosen. 1-6 In summary, if the heat-flow type approximations are to include the terms arising due to convection, one of several choices may be made: (1) an upstream (to the direction of flow) approximation for the convection terms may be used; (2) a centered-in-distance (CID) approximation may be used; or (3) a recently developed approximation based on the theory of oscillation matrices may be chosen.6 The last appears to have significant promise for one-dimensional flow problems; its extendibility to two or three dimensions is an open question. In either of the first two approaches, a suitably small ratio of v&/D must be maintained, where v is the velocity, & is the grid spacing and D the effective dispersivity in the direction of flow. In the first choice, the approximation of the convective part is only first-order correct and errors introduced appear as a numerically induced dispersivity of magnitude proportional to v?x. In the CID choice, the approximation can be second-order correct, but the difference formulation fails to satisfy the maximum principle unless a condition on v?x/D is met. Practically, this means that for high flow rates oscillatory solutions may result in the neighborhood of a front unless exceedingly small grid intervals are taken. While the procedure proposed by Stone and Brian4 permits a less severe limitation to be placed on this ratio, ultimately the flow rates increase relative to the dispersivity the oscillation obtains. Further, extensions of their approach to higher dimensional systems may be attended by considerable

Jan 1, 1967

By D. E. Baldwin

A method has been devetoped for predicting the produced concentration profile for a miscible slug in a five-spot pattern. The technique consists of dividing the five-spot into radial etements and applying an approximate radial solution of the dispersion equation to each element. To test the method, laboratory experiments were conducted in five-spot models. The models were 2-ft X 2-ft X 2-in. Berea sandstone slabs simulating one quarter of a five-spot. An aqueous system was used with tritiated water as the tracer fluid. Effiuent concentration profiles were obtained for slug sizes ranging from 0.7 to 10.2 per cent of the pore volume. Agreement between predicted and experimental profiles was excellent. A prediction was also made for a field tracer test. For this case the predictive technique was modified to account for stratification by use of a layer cake model. INTRODUCTION Dispersion in porous media is of growing interest to the petroleum industry because of the increasing importance of secondary recovery operations. One of the controlling factors in the recovery of oil by miscible displacement or by the use of waterflood additives is the degree of mixing between the fluids of interest. Consequently, one of the prerequisites of any recovery prediction is an adequate method of predicting dispersion. Also, any quantitative interpretation of waterflood tracer tests is dependent upon the ability to determine the dispersion of the tracer as it flows through the reservoir. During the past few years there have been reported in the literature the results of a large number of investigations, both theoretical and experimental, concerning dispersion in porous media. (An excellent review of these results has been presented by Perkins and Johnston." Only a few of these investigations, however, deal with non-lin-ear flow systems. Raimondi et al.9 have presented an approximate solution of the dispersion equation for radial, diverging flow. Lau et al. 7 and Bentsen 1 have presented laboratory data for radial systems and have shown that the dispersion can be adequately predicted by Raimondi's solution. Bentsen has also presented a small amount of data for a radial, converging system. Brigham and Smith' have applied Raimondi's solution, with approximating assumptions, to a five-spot pattern to predict the behavior of a field tracer test. The afore-mentioned investigations have been concerned almost entirely with radial diverging flow and have neglected the effect of converging flow. For this reason the present investigation was undertaken to develop a method of predicting dispersion in a five-spot pattern including the effects of both diverging and converging flow. The method which was developed consisted of dividing the five-spot into diverging-converging radial elements and applying an approximate solution of the disperson equation to each element. DEVELOPMENT OF PREDICTION METHOD The development of the prediction method consisted of two phases: construction of a radial model of a five-spot pattern and derivation of equations to describe the dispersion in the radial model. FIVE-SPOT MODEL A radial model which simulated the flow characteristics of a five-spot pattern was constructed by dividing the five-spot into diverging-converging radial elements (Fig. 1). Because of symmetry the model represented only an octant of a complete five-spot. Each element had an included angle of l° (making a total of 45 elements) and a radius r, such that the sum of the individual element areas was equal to the area of the five-spot octant. The normal five-spot fractional flow behavior was determined by averaging the experimental five-spot data of Caudle and Witte,' Dyes, Caudle and Erickson 5 and Fay and Prats. 4 The resulting curve is shown as a solid line in Fig. 2. To match this curve with the radial model it was

Jan 1, 1967

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,' research on the subject is still in an early stage of development."' To the authors' knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal's position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.' Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By W. C. Knopf, G. Samsel

For several years International Minerals & Chem-ical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large-scale plants. Natural potassium is composed of three isotopes —K, K and K. Five other isotopes, artificially produced, have been detected. In natural potassium only the K isotope, with a half life of 1.4x10 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes. Barnes and Salley' measured radiation of potassium salts in solution in 1943. Gaudin and Parnell2 first reported the use of solid salts arranged in a vessel surrounding the ß counter in 1948. Later, Scheel used the method to assay potassium content of various crude and finished potash salts. Experimental: Dip-type Geiger-Muller tubes (TGC-5) supplied by Tracerlab Co. were used in all radiation counting measurements. The tube was encompassed by a glass container about M in. larger in diameter than the tube. This container, which served as a sample holder, was closed at the bottom with a rubber stopper to facilitate removing the samples. Samples were not weighed, but about 40 g of sample were needed for each test. Electrical impulses from the tube were counted on either a Tracerlab scaler or a rate meter. To obviate the need for constant attendance, preset features were incorporated into the scalers, so that at a predetermined time or count the units were automatically deactivated. When rate meters were used, counting rates were read directly from instrument or from a recorder used in conjunction with the rate meter. Each tube was calibrated, according to the manufacturer's instructions, to determine the correct operating voltage to insure reproducible results. A linear calibration plot of percent K2O vs counting rate was also obtained for each tube by recording the counting rate plus background count of several standards of different K2O content chemically analyzed by the chloroplatinate method.' These standards were of approximately the same particle size distribution as samples to be assayed. Specific background count caused by cosmic rays and other surrounding radiation was checked periodically by counting a sample of pure NaCl. Fig. 1 is a representative calibration plot. Assays were determined directly from the standard plot or calculated by subtracting the background count from the counting rate, then multiplying by the slope of the line. Chemical assays of the test samples were made by the Sherril method," a flame photometric technique, or the chloroplatinate method. Data: The radiation assay method has been used for three years by International Minerals & Chemical Corp. in the laboratory and in pilot plants processing ores containing potassium. These dry concentration plants process sylvinite and langbeinite ores at Carlsbad, N. M., and feldspar ores at Top-sham, Maine. Sylvinite ore is predominantly a mixture of syl-vite (impure KCl) and halite (impure NaCl). Contaminants include sulfates, such as langbeinite (2MgSO - K2SO4), kieserite (MgSO H2O), poly-halite (MgSO4.K2SO, 2CaSO, . 2H2O), and slimes. Langbeinite ore is predominantly langbeinite and halite with small amounts of sylvite, sulfates other than langbeinite, and slimes. Several variables, in addition to correct calibration and standardization of tubes, were found to be important in obtaining reproducible results. Particle size distribution of standard samples should be

Jan 1, 1959

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

Jan 1, 1934

By George T. Wickes

(Washington Meeting, May, 1905.) SEVERAL years ago, Mr. Robert A. Cook described and illustrated in our Transactions 1 a mechanical coke-drawer, patented in 1891 by Mr. Thomas Smith of the Thorncliff Iron Works, Sheffield, England, and first introduced in the United States in, 1896, at the coking-plant of the Latrobe Coal Co., Latrobe, Pa. This machine has not received any very extended application in this country, although it was successfully used in two places for a number of years. The present. paper describes a new and simpler machine, containing few wearing-parts capable of withstanding continued rough usage. Anything which tends to prolong the general use of bee-hive ovens will be welcome to those who are interested in cheapen¬ing the cost of producing coke in such ovens, especially if it provides satisfactory mechanical means, replacing the hard labor involved in drawing coke by hand with the old-fashioned ?duck bill.? The difficulty of finding efficient coke-drawers, especially during the summer season, and in the South, is notorious. Yet, notwithstanding the great improvements that have been made in retort coke-ovens, new bee-hive ovens are continually constructed; and a machine which will successfully compete with hand-drawing, and, at the same time, add to the efficiency of the bee-hive oven, seems to deserve notice. The machine here described was put in operation at the Frick Coal and Coke Co.'s plant, known as Continental No. 1, at Uniontown, Pa., in October, 1904, and is reported to have met successfully all the tests to which it has been subjected. This trial has demonstrated that one of these machines, equipped with an electric motor, and operated by one mart with an assistant, besides two men to " water down " the

Jul 1, 1905

By AIME AIME

WILLIS McGERALD PEIRCE-"Jerry" to his host of friends, and on that account a hit of a puzzle to those who have known him only as "W. 14."-a native of Buffalo, educated at Penn State College, Illinois: and Yale universities, has bee11 associated throughout all of his professional career with the New Jersey Zinc Company. Jerry has served successively as investigator, section chief, and division chief in the research department of the company and has just been promoted to chief of research.

Jan 1, 1937

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By Lewis T. Wright

(Pittsburg Meeting, March, 1910.) I HAVE long been aware that ferruginous copper furnace slags if fused in the electric arc will yield metallic iron containing copper, and in order to confirm this knowledge, and to obtain further information of the behavior of such slags in the high temperature and reducing conditions of the electric furnace, a number of samples of slag were fused in an experimental electric furnace. The results obtained, given in Table I., show that a very large amount of metallic iron was produced, and that this iron carried with it practically all the copper, gold, and silver, and more than 50 per cent. of the sulphur, of the original slag. The metallic buttons formed in the electric furnace were clean, hard, but not brittle.

Mar 1, 1910

By J. Randel Hill

The 64th Texas Legislature passed the "Texas Surface Mining and Reclamation Act," Chapter 131, Texas Natural Resources Code (subsequently referred to as "the Act"), at a point in time when little surface mining had taken place within the state. Thus, enactment of regulatory control governing mining operations in our state has, for the most part, preceded widespread, intensive mining activity. I should point out that the statute applies only to the extraction of coal, lignite, uranium and uranium ore. A recent opinion rendered by the Attorney General's office has stated that extraction of the named elements, when it occurs incidental to the extraction of other materials, e.g., clay, is not not an activity subject to the Act. An important theme of the Act, frequently overlooked in other environmentally oriented legislation, is recognition of the Act's affect on the mining industry. The Act states that "the extraction of minerals by surface mining operations is a basic and essential activity making an important contribution to the economic well-being of the state and nation" and, in reference to reclamation being accomplished contemporaneously with mining, provides a recognition that "the extraction of minerals by responsible mining operations is an essential and beneficial economic activity." This legislative recognition is, of course balanced against the need for proper mined land reclamation, the rights of surface owners, the need to guard against unreasonable degradation to land and water resources and numerous other actions or events that the Legislature wanted protected. Another rather pervasive general theme that is established in the Act is the concept that the agency is entitled to obtain whatever information, or take whatever action, that appears reasonably necessary to effectuate the purposes of the Act. This concept, coupled with the detailed requirements placed on mining operations in the portions of the Act dealing with Permit Applications, Reclamation Plan and Reclamation Standards, easily insures that surface mining activities can and will be regulated to the extent necessary. Section 131.102(b)(2) is probably the most relevant provision in the Act which deals with the preclusion of mined lands becoming waste lands. This portion of the Act states that the surface mining operator shall: ". . . restore the land affected to the same or a substantially beneficial condition. ." In this language the Legislature had made it abundantly clear that the abandoned or orphaned lands found in some of the Eastern states, will not be tolerated in this State, and provided the Commission with a degree of latitude to determine what condition would be appropriate in each individual mining situation. I bring this area of the Act to your attention because it is the area which has received the most inquiries and concern by operators, i.e. what does "substantially beneficial" constitute? The Commission's staff has spent a considerable amount of time wrestling with the statutory language "substantially beneficial" to determine the legislative intent and provide operators with guidance of what they can expect. In this regard, the most definitive criteria in our opinion lies in the Act's legislative hsitory. The Legislature had before it basically three reclamation standards namely: House Bill 656, considered to provide the most stringent reclamation standard and identical to Senate Bill 66; House Bill 1717 which was supported by industry spokesmen and was considered to contain the least stringent reclamation standard; and Senate Bill 55 which was adopted by the Legislature. During the Bill's initial hearing before the House Environmental Affairs Committee, the House sponsor of the Senate Bill 55, which was the Bill eventually adopted, made the following statement: (I am quoting verbatim from the Committee's transcript although substituting the speaker's reference to the authors names with the Bill's numbers.) "An example of the differing approaches of the four bills can be seen in the area of reclamation standards and this is critical. House Bill 656, talking about restoring the surface of the land, House Bill 656 has this statement: 'At least fully capable of supporting the use to which it was capable of supporting prior to any mining or any higher or better use.' In other words you have to restore it to the level it was prior to the mining. Senate Bill 55: 'Restore the land to the same or substantially beneficial use.' Substantially beneficial use. (Emphasis his) House Bill 1717 says: 'Restore insofar as practical to appropriate beneficial post-mining use.' So that House Bill 1717 said to, 'restore insofar as practical to appropriate beneficial use. I think that's too weak, whereas I think the House Bill 656 that would call you to restore it to at least the use it had prior to the mining may also be too tight the other way. I think the Senate Bill 55 approach is down the middle of the road which says that you do restore it to the 'same or substantially beneficial use,' is a proper way to go there." Therefore, the conclusion that we have drawn from the legislative history of the bill is that the extent of reclamation required by "substantially beneficial" may be something other than the use it was prior to

Jan 1, 1979

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By John B. Myers

VERMICULITE is a name used to describe micaceous material that exfoliates when heated. It is hydrated magnesium-aluminum-iron silicate. The chemical composition, color, physical appearance, and degree of exfoliation vary. COMPOSITION, PROPERTIES, AND ORIGIN Vermiculite has the characteristic micaceous structure of basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. Hardness is 1.5; specific gravity, 2.2-2.7; luster pearly to greasy; colors, amber, bronze, reddish brown, dark green, and black. Feel is soapy, particularly when wet. When heated it exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin veamiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted into steam. Warping of the unit layers may also contribute to the expansion. The increase in bulk volume of commercially prepared material is 8 to 12 times but individual flakes may increase in size more than this. Pure vermiculite is a distinct mineral and has the structural formula (OH), (Mg,Fe)3 (Si,Al,Fe)4 010.4H20. It rarely occurs in this pure form, but generally as a mixed mineral of varying structure. One explanation is that the mixed material is composed of unit layers of inter-stratified pure vermiculite and biotite. The essential difference between the two is that unit cell structure of vermiculite contains a layer of water molecules whereas the biotite cell contains potassium instead of the water. The water content of the mixed vermiculite is less than that of pure vermiculite but more than that of biotite. Pure biotite does not expand when heated. If the proportion of biotite layers in a vermiculite is too high it will adversely affect the degree of exfoliation. Within a given deposit, the great mass of material may approach a definite com-position with local areas of greater biotite content. It is not uncommon to find also small pockets of pure biotite but these are generally segre-

Jan 1, 1949

By G. A. Merkt

THE Isley furnace control, here presented as a novelty in furnace construction, is, in principle, one of the oldest methods of maintaining furnace heat for industrial purposes. Records unearthed in Egyptian tombs and the primitive methods of melting metal practiced by African tribes today indicate that fanning the fire and forcing the furnace by bellows have been an effective means of regulating heat for man's work during thousands of years. Even today, these cruder forms of mechanical draft production are still nn use within the borders of this most highly developed industrial land. Stacks, as we know them, are of com- paratively recent historical age but their attractive simplicity and seeming effectiveness have made them exceedingly popular. And so we find one of the most important types of furnace the world has even known, the open-hearth furnace, duly and more or less properly equipped with a chimney. The regenerative, or reversing, type of furnace, how-ever, required another mechanism between its hearth and the stack to provide a means for alternately con-necting one side and the other of its system of regen-erative chambers and flues to the stack and to a source of fuel and air supply respectively. Various types of reversing valves were developed, some of which are re-markably well designed for maximum efficiency and ease of installation as well as operation. However, this combination has a number of inherent faults which are so difficult to correct as to make efforts in the direction of improving over-all efficiency almost futile. These inherent difficulties are as follows: (1) The necessarily high temperature at which the gases must be delivered to the stack in order to make it operative. (2) The great temperature difference incidental to the reversal of flue gas and air and consequently the large variation in preheated air and fuel delivered to the furnace dur-ing the cycle. (3) The leakages and resistances created by the reversing apparatus and the complicated flues necessary. (4) The inadequate range of control af-forded by the natural draft system, especially under adverse atmospheric conditions.

Jan 12, 1927

By W. R. Ingalls

THE bases of the work by the committee whereof I am chairman were (1) the abolition of extra-lateral rights and (2) the preservation of the maximum of the existing laws. The matter of extra-lateral rights had been under prolonged discussion among mining men and up to the time when our com-mittee began its work (in 1917) the expression of opinion in every way whereby it could be made known -and those ways were extensive-was only a little short of being unanimous that extralateral rights ought to be abolished. I have not observed important evidence indicating a change of opinion on the subject since 1917. ABOLITION OF DISCOVERY LOGICAL Now, when it be decided that extralateral rights ought to be abolished, there can not be merely a simple change to that effect, but it is found that consequential changes are necessary all the way through the existing laws. Abolition of extralateral rights implies abolition of discovery as a prerequisite to location, for otherwise there would be no legal means for locating claims on the dip of a vein. Quite apart from this consideration, abolition of discovery as a prerequisite to location is supported by other good reasons. Among these are the occurrence of orebodies with no exposure on the surface and which often are hidden at great depth. A prospector who has reason to suspect the occurrence of such an orebody must have legal means for the location of a claim within which to explore, and obviously he may. not be able to make any discovery on the surface sufficient to locate and hold legally such a claim under the terms of the law as it stands at present. As a matter of fact, discovery as a prerequisite to location was abolished by common consent many years ago, not only for the reasons that I have given here-inbefore but also for others. It is highly desirable to revise the mining law in this respect, so that it will conform to the conditions of practice and not require people to perjure themselves in making locations, even if it be for praiseworthy purposes.

Jan 6, 1922

By Howard Evans

Moderate but substantive gains were recorded in 1972 in the minerals processing industry. In the area of mill design, a number of large plants under construction during the past two to three years were tuned up and went into production. The application of operating controls has also made some significant strides. Progress here has been made in the areas of on-stream particle size analysis, on-stream x-ray analysis, slurry transportation, tripper control, flotation reagent control and digital control of grinding circuits. The major contributions to improved equipment are coming from smaller specialized equipment makers.

Jan 2, 1973