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By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By F. W. Glaser, Benjamin Post

A LTHOUGH most transition metals form a wide variety of boride compounds, the existence of only one zirconium boride, ZrB2, had been established prior to this investigation.' The crystal structure and some properties of a hitherto unreported zirconium boride, ZrB12, are described in this paper. Only one other dodecaboride of a transition metal, UB12, has been reported up to the present.' Chemical analysis of the new compound showed 44 pct Zr and 56 pct B, compared with 41 pct Zr and 59 pct B computed for ZrB12. The difference is within the range of error of the analytical method employed. ZrB12 shows marked metallic properties. It is obtained as a fine black powder. Measurements of electrical resistivity were made at —79°C, + 22°C and +64°C. At 22°C the electrical resistivity is approximately 60 microhm-cm. Over this range the temperature coefficient of resistivity is +0.00162. The thermal conductivity at room temperature is 0.122 watts per cm per "C. The product of the electrical resistivity and thermal conductivity is therefore 8.05, which is not far from the normal Wiedemann-Franz ratio (approximately 7.5 at room temperature). These measurements were made on hot pressed samples which were not always high density specimens. The hardness of ZrB12 on the Rockwell A scale varies between 92 and 92.5. Crystal Structure Determination Single crystals of ZrB12 of a size suitable for X-ray diffraction analysis could not be obtained and powder samples had to be used. Filtered Cu radiation was used throughout. Powder diagrams were indexed on the basis of a face-centered cubic unit cell. After correction for film shrinkage, a Bradley and Jay extrapolation³ to ? = 90" indicated that a, = 7.408 ±0.002A. The volume of the unit cell is 406.5A.V he assumption that there are four "molecules" of ZrB12 per unit cell leads to an X-ray density of 3.63 g per cc. The measured density is 3.7 g per cc (as measured by the immersion method). Relative intensities of reflections were determined by integrating the intensities of diffraction peaks using the count register of a North American Philips wide range spectrometer. Intensities measured in this way showed good agreement with photographic intensities estimated visually using multiple film techniques. The usual Lorentz, polarization, and multiplicity corrections were applied to the observed intensity measurements. There are striking similarities between ZrB12, and UB12. The unit cell of the latter is also face-centered cubic and contains four molecules. a, = 7.473, compared with 7.408 for ZrB12. The radius ratio rB/rU is 0.57; rB/rZr is 0.54. In both ZrB12, and UB12 the four metal atoms in each unit cell are in special positions; only the boron positions need be determined. The latter may be inferred from the extent to which diffraction of X-rays by the 48 boron atoms reinforces or weakens the diffraction by the metal atoms. This effect is relatively much greater in the case of the zirconium compound. In their determination of the crystal structure of UB12, Berthaut and Blum' assumed holohedral symmetry (space group Oh5 , Fm3m) and reported that the U atoms are in positions 4(a): 000; 01/2 1/2; ½ 0 ½ ; ½ ½; the boron atoms were reported to be in positions 48(i) with x = 1/6: ½xx; ½xx; x½x; x½x; xx½; xx½; ½xx; ½xx; x½x; x½x; xx½; xx½

Jan 1, 1953

By A. T. Corey, J. H. Henderson, M. R. J. Wyllie, C. H. Rathjens

The results of three-phase relative permeability tests on nine water-wet consolidated Berea sandstone samples are presented as composite ternary diagranls showing isoperms of oil, water and gas. Capillary pressure control was exercised over the flow of gas and oil in the presence of water. The water saturations ranged from 17 to 71 per cent pore volume. A method of calculating both the oil and water permeabilities of a three-phase system from the easily measured gas relative permeability is presented. EXPERIMENTAL PROCEDURE AND RESULTS A renewed interest has been shown in three-phase relative permeability as a result of recent developments involving underground combustion processes, steam injection, and other multiphase displacement processes. The experiments and results described here involved simultaneous flow of oil and gas in consolidated Berea sand with brine present as the wetting phase. Gas and oil relative permeabilities were measured on nine cores with CaC12 brine present as the wetting phase in saturations ranging from 17 to 71 per cent. The average residual liquid saturation of the cores was approximately 20 per cent. In order to make certain that brine was the wetting phase, the test cores were saturated with brine before contact with hydrocarbons. As an added precaution to avoid having oil displace brine from the wetting position as a result of changing wettability, each core was only used twice, i.e., first with a fixed percentage of brine and then for a gas-oil permeability determination with no brine present. The results, therefore, are presented as composite ternary diagrams representing the flow tests on nine individual cores having very similar properties. All tests were made using a modification of the capillary pressure techniquc described elsewhere. The effective oil permeability was measured before gas was introduced using a very small pressure gradient (a few centimeters of oil). This determination was made without selectively wet barriers in contact with the core. The cores were then placed between capillary barriers and gas-oil relative permeability curves obtained. The capillary barriers had been made water repellent with a silicone treatment. In determining gas-oil-water relative permeability in this fashion, control was exercised over the capillary pressure existing between the gas and oil. No control was exercised over the pressure difference existing between the oil and water. Athough an equal pressure gradient was applied to the gas and the oil phases, this pressure gradient does not exist in the water phase. Since the pressure gradient across the core was always much less than the displacement pressure of the fully saturated core, the pressure gradient can have caused only a very slight distortion of the oil-water interfaces. This slight distortion of the oil-water interfaces had a negligible effect on the validity of the oil permeabilities measured. The oil permeability, measured in the presence of water but with no gas present, was in every case equal. within experimental error, to the gas permeability of the gas-oil system when the oil saturation was the same as that of the water. Gas and oil relative permeabilities were plotted as a function of total liquid saturation. It was found that the gas relative permeability curves obtained on cores with brine present were identical with those obtained on the same cores with no brine present. The denominator for calculating oil relative permeabilities was the permeability found by extrapolation to infinite mean pressure (A la Klinken-berg). Fig. 1 illustrates gas-oil relative permeability results obtained on a typical core. The solid permeability curves represent the experimental data. The dashed oil relative permeability curve was calculated using the relationship;

Jan 1, 1957

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By Christian F. Baiz

INTRODUCTION Industrial minerals can have similar financing requirements to those needs of metaliferrous and coal mining projects. One of the outstanding differences is the understanding of the many different markets that these industrial minerals represent. There are in excess of 30 principal industrial minerals ranging in terms of annual production from the largest quantity such as sand and gravel, to possibly the smallest quantity of production of a legitimate industrial mineral which may be defined as industrial and rough gem diamond. (See Tables 1 and 2) Project finance techniques, analytical methods, and information requirements are covered elsewhere in this Chapter and Chapter 10. Some comments on equity finance aspects follow. EQUITY AMOUNT The amount of equity in a financing transaction provides a cushion to the lender in case the project runs into trouble. Generally speaking, the greater the amount of risk in a project, the more equity a lender will require. The amount of cash equity in a project financing transaction is between 25 and 40 percent. The amount of leverage (debt/equity) is negotiable based on such factors as the strength and extent of the sponsor's undertakings, of the project's economics, and the term of a strong sales contract. Naturally, a borrower seeks to obtain d loan with as little equity required as can be negotiated. Zero percent equity is usually associated with a take-or-pay contract (a hell-or-high- water unconditional commitment under which the purchaser must pay for the commodity as though it were shipped regardless of whether it is actually mined or shipped) with a financially strong corporate entity i.e., the parent company or an end user. As a take-or-pay contract is tantamount to a guarantee of payment, the banker views the credit basis of the loan as being other than the borrower's mining operation and therefore will analyze the creditworthiness of the institution purchasing the commodity on the basis of its corporate balance sheet. Do not confuse a take-or-pay contract with a take-if- tendered or take-and-pay contract. Another means in the United States of obtaining zero percent equity is the carved out production payment financing, typical of coal mine financing. This involves the sale, or conveyance, by the owner of the mineral property of a production payment to a nominally capitalized company. The nominally capitalized company is formed solely to buy the production payment and usually borrows 100 percent of the purchase price from a lender. Equity amounts of 10 to 20 percent generally are found in transactions which employ techniques such as an advance sale or a subordinated lease/loan. These agreements are viewed as quasi equity by most banks for several reasons. First, the proceeds represent a cash infusion early in the project's life - usually prior to the bank lending any funds. Thus, the repayment schedule is "behind" that of the bank debt. In the case of an advance sale, repayment is in the form of a long-term supply contract with favorable terms, usually priced close to the mining operation's costs. There is also usually a requirement that all costs of the project be paid for by the loan or equity, often making the sponsors financially responsible for any cost overruns. Cost overruns are a major risk in any project, large or small, and are often due to unforeseen factors such as wildcat strikes, a piece of faulty equipment, or any event which delays completion, e.g., remote location, weather, etc.. . The question of how overruns are covered can be negotiated. For example, in addition to the original debt/equity ratio of the project, there can also be a cost overrun ratio that will

Jan 1, 1985

By Ed L. Reed

INTRODUCTION The most efficient development of a mine plan for in-situ leach (solution) mining must be based upon an understanding and application of the basic hydrologic characteristics of the aquifer containing the mineral values. Similar knowledge of the overlying and underlying aquifers is also required. This paper summarizes the hydrologic properties of a ground water system and describes some of the more important conclusions that can be drawn from a detailed hydrologic study. Basic to an in-situ leach mining operation is the flow of fluids through porous rock from place to place. The degree to which these movements of fluids can be predicted and controlled determines to a large extent the efficiency of the ore recovery operation. HYDROLOGIC CHARACTERISTICS The principal hydrologic characteristics of a porous medium (sand, intercrystalline or vuggy limestone, fractured basalt, etc.) influencing fluid flow are: Porosity Permeability Thickness Transmissivity Storage Coefficient Water Table or Piezometric Surface Hydraulic Gradient Briefly these parameters can be defined as follows: Porosity: the void space in a unit volume of rock. Permeability: the ease with which fluid will flow through a porous medium. Thickness: the height of the formation which contributes flow to a well. Transmissivity the product of permeability and thickness. Storage Coefficient. the volume of water released from the reservoir per unit drop in head. Water Table or Piezometric Surface: the level at which water will stand in a well: the top of the zone of saturation in a gravity aquifer; the height to which water will rise above the confining bed in an artesian system. Hydraulic Gradient the direction and rate of dip of the water table or piezometric surface. A properly designed pumping test will provide numbers for transmissivity, storage coefficient and the water table or piezometric surface. Drilling records or bore hole logs provide aquifer thickness data from which permeability can be calculated. Ground elevations applied to measured depths to water enable one to calculate the direction and rate of dip of the water table or piezometric surface. Porosity can be determined from core analyses or density logs; it can be estimated from grain size distribution curves in sands or sandstones and from, microscopic examination of drill cuttings derived from carbonate aquifers. CHARACTERISTICS OF FLUID FLOW The characteristics of fluid flow that are vital to an understanding of leach mining include: Velocity Direction Flow Path Radius of Influence The velocity of fluid flow is of paramount importance in planning and managing a leach mine operation. Velocity is directly proportional to the permeability and hydraulic gradient and indirectly proportional to the effective porosity The permeability determined from a pumping test is an average value for the interval stressed; therefore, the velocity calculated from data derived from a pumping test represents average conditions. Under actual conditions discrete portions of the aquifer open to the screen may have permeabilities several times as high as the average and minimum permeabilities only a fraction as much. An injection front will be irregular to the extent that the reservoir rocks are heterogeneous An important consideration is the direct relationship of velocity to head. A reservoir which would provide a velocity of 0.05 feet per day under conditions of equilibrium would allow fluid flow of 36 feet per day under typical leaching operations, i.e. 12-foot injection head, 12-foot pumping level and 50 foot five-spot pattern. The direction of fluid flow is also vital both inside and outside the mine area. In the pattern area the direction of flow is determined by the geometry of the well field and can be approximated by mathematical modeling techniques. Outside the well field, the direction of flow is influenced by both natural conditions and the degree to which production and injection volumes are balanced. Flow directions (and velocities) are critical to an understanding of leachate excursions and their control.

Jan 1, 1979

By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method' devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o'clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By C. F. Baes, H. H. Kellogg

The effect of dissolved sulphur on the surface tension of liquid copper has been measured by a sessile-drop method at 1120°C. Sulphur is highly "surface active" in liquid copper; the surface tension lowering is about 650 dynes per cm for a sulphur content of 0.6 pct. The degree of adsorption of sulphur on the liquid copper surface has been calculated, and various models of the surface layer have been tested against the results. THE science and technology of surface chemistry and physics at room temperature are relatively advanced, and the engineer possesses a background of information that allows him to predict and control many phenomena—such as frothing, emulsifica-tion, wetting of solids by liquids, flow through capillaries, adsorption, mineral flotation, penetration of porous bodies by liquids—which are related to the behavior at interfaces. Surface phenomena in high temperature systems are probably of equal importance to the metallurgist and ceramist, but at present are incompletely understood. Frothing of liquid slags, penetration of refractories by liquid metals and slags, infiltration of powder metallurgy "skeletons" by liquid metals, bonding of metals to ceramic oxides in the manufacture of "cermets," wetting of one metal by another for purposes of soldering and welding, are but a few of the many phenomena of metallurgy that are controlled by surface behavior. Concerning the most elementary of surface properties—the gas-liquid surface tension—the existing data on liquid metals are inadequate. For the surface tension of "pure" metals the results of different investigators differ by 10 or 20 pct. The role of surface-active agents in liquid metals is relatively unknown, and it is not unlikely that the discrepancy in the values for the surface tension of pure metals is due to the presence of traces of surface-tension-lowering impurities in the samples. Based on analogy to room-temperature systems, the highly surface-active impurities in liquid metals should be elements or compounds of limited solubility in the liquid metal and possessing considerably weaker in-termolecular bonding forces than the metal itself. The nonmetals of the V, VI, and VII groups of the periodic table might be expected to act in this way. The experimental work in this paper represents a study of the surface tension of pure liquid copper in hydrogen at 1120°C, and the effect of dissolved sulphur (which is a strongly surface-active agent in liquid copper) on the surface tension of copper. The Gibbs equation has been applied to the results and an attempt made to correlate the surface tension behavior with two models of the interfacial layer. The sessile-drop method for surface-tension measurement at high temperatures which was used in this investigation has been described by several investigators.1,2 It involves the measurements of the dimensions of a stationary liquid drop on a horizontal surface. From these dimensions and the liquid density, the surface tension of the liquid may be calculated either by means of various approximate formulas, or more accurately by means of the Bash-forth and Adams tables.- or liquid drops which exhibit a contact angle greater than 90°, by far the simplest dimensions to measure are those indicated in Fig. 1, i.e., the diameter of the maximum horizontal cross section (2X) and the maximum height (Z) above this plane. In order to calculate the contact angle and the volume of the drop, the diameter at the base of the drop (2a) and the total height (h) also must be measured. Upon investigation of the literature, the authors failed to discover a concise statement of the accuracy of the method when used in conjunction with the Bashforth and Adams tables, hence a careful examination of the tables was made and the curve shown in Fig. 2 was constructed. The "error factor," plotted as the ordinate, is the factor by which the

Jan 1, 1954

By D. L. Everhart

The search for new deposits raises two important questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? A review of the wide geological variety of recent uranium discoveries tells how these questions are being answered. SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the overall job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Compared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits. One of the most interesting features of known uranium deposits of the world is the wide variation, see Table I, in character and geologic environment. It should be noted that many types became prominent during 1953. The davidite-bearing veins of Radium Hill, South Australia, are almost unique, although the same mineral occurs in a different kind of deposit in Mozambique. Recent studies indicate that brannerite disseminated in the granite near Cracker's Well, South Australia, may soon constitute uranium ore. Basalt has been added to the list of favorable host rocks in the Northern Territory of Australia. Basalt is also the host of the pitchblende veins of the Martin Lake deposit, Beaverlodge district, Saskatchewan. The truly remarkable rich and extensive Steen deposit near Moab, Utah, is of the uraninite-vanadium oxide type. Secondary hydrous uranium arsenates and phosphates constitute the uranium minerals in the disseminated deposits of the Wind River Basin, Wyo., a new district discovered in the summer of 1953. Uranium minerals in shales adjacent to fractures were newly reported in New Mexico and several other parts of the world during the year. The well-known important uraninite dissemination in the Rand conglomerates of South Africa has a counterpart, as discovered in the summer of 1953, in the Mississagi quartzite and conglomerate of the Blind River district, Ontario. Gunnar deposit of the Lake Athabaska district, Saskatchewan, consists of uraninite in both granite and sedimentary gneiss beneath a granite cap, and large new orebody of the Eldorado Co. in the same general area follows a preferred stratigraphic horizon in schists. Uranium is, generally speaking, a very soluble and ubiquitous element. It occurs in at least two valency states and for this reason is not easily tied down in natural solutions. As Gruner' has pointed out, it is probable that uranium starts in the hexava-lent state in nearly all solutions instrumental in its transfer. It is believed that under oxidizing conditions the uranium moves in solution as the uranyl ion, UO. In solutions ranging in pH from 1 to 5, the uranyl ion is most commonly in association with

Jan 1, 1955

By U. N. Bhrany, N. Arbiter

F. C. Bond (Consulting Engineer, Processing Machin-Dept., AllisChalmers Manufacturing Co., Milwaukee) This is a very comprehensive paper. It deals with 1) size distribution functions, 2) energy-particle size relationships, and 3) criteria for grinding efficiency. The method of analysis used consists of tracing the increase and decrease of successive Tyler scale screen fractions as grinding progresses. The treatment is based upon the assumption that the work done in grinding is concentrated entirely upon the coarse size fractions in the mill. It is postulated that when a feed consisting entirely of particles of one size fraction is batch ground that finer fractions increase at a constant rate as grinding progresses, until finally each in turn begins to be ground and to decrease in amount. It is shown that under these conditions the empirical Gates-Gaudin-Schuhmann log-log size distribution plot can be logically explained. It is difficult to imagine any condition of ball mill operation, or any probability analysis, which would result in no grinding contacts on the finer particles present. However, the authors' postulate must be accepted if their conclusions are to be sustained. They conclude that the equation expressing the for mation rate of each size fraction can be resolved into the G.-G.-S. size distribution equation, and that the curvilinear portion of the log-logsize distribution line represents the only particle sizes which are being ground as well as produced. The author's statement that the G.-G.-S. Eq. 4 applies only to the finer portion of the size distribution while the Rosin-Rammler Eq. 6 applies over the whole size distribution range certainly supports the view that an exponential equation of the Rosin-Rammler type corresponds more closely to actual size distribution than does the power law G.-G.-S. equation. However, the G.-G.-S. equation is used to derive Eq. 8 and Eq. 9, which state that the energy required to grind a ton through a particular mesh varies inversely as the particle size to the exponent -a , whic h is the slope of the extended G.-G.-S straight line. This is stated to apply to both batch and continuous grinding. The G.-G.-S. slope exponent thus becomes very important in all crushing and grinding analyses by this method. The authors include some data which can be used to test their conclusions, as described below: We will consider grinding a feed composed of 14 mesh (1190u) to -200 mesh (74u). The average of 17 Allis-Chalmers grindability tests on quartz gives a work index (Wi) of 12.77. The -200 mesh product should have 80 pct passing 41.6u or P = 41.6. The equivalent 80 pct passing size of the 14 mesh feed particles is considered to be the particle diameter, as is true for spherical particles. Thus F is 1190u. In the work index equation 10 wi 10 wi 127.7 127.7 P f 41.6 1190 = 16.1 kw-hrperton. In Table I the ball mill exponent for quartz is 1.0 and from Eqs. 9 and 10: w=kw-hr/ton =Constan/(do/di) = 16.1 ton so that (1190) Constant/ Constant and the Constant equals 259. The tons per horsepower-hour value is 0.0464, in agreement with Table IV. The exponents for other minerals are listed in Tabl e 11. In Table IIA, the kilowatt hours per ton required to grind these minerals between the same sizes as the quartz, both by the authors' method and the work index equation, are listed. According to the authors kw-hrperton = 259/(16.1)".

Jan 1, 1961

By F. W. Jessen, James N. Howell

INTRODUCTION The determination of cloud points has to date been limited to rather transparent oils, visual observation of the formation of a solid phase being the criterion for the standard ASTM D 97-47 method. The need for a quiclc and simple method for determining cloud points under dynamic conditions for opaque crude oils became necessary in a study of fundamental aspects of paraffin deposition from crude oils. PREVIOUS WORK The determination of cloud points in opaque oils by viscosity temperature curves is fairly new, Young' described a method employing the capillary tube principle. No information exists relative to the determination of cloud points of crude or refined oils under dynamic conditions. Shock' noticed that deposition of paraffin from crude oils took place at temperatures at or below the temperature at which a sharp inflection point occurred in the viscosity-temperature curve. This observation indicates a possible correlation between this temperature and the cloud point of the crude oil. Reistle and Vietti1 have reported that when crude oils containing small amounts of asphaltic materials were heated to temperatures sufficiently high to solubilize these materials and immediately cooled the pour point of the crude oil was lowered as much as 70°F. Sachanen\ asribes this effect to the action of colloidal asphaltenes in preventing the formation of the crystalline structure necessary to maintain the oil in a rigid state. At high temperatures, asphaltenes are peptized, and the paraffin crystals formed at these temperatures adsorb the colloidal asphaltenes on their surface thereby hindering further growth of the crystals. Reistle" found, however, that such heating and cooling of crude oils had no effect upon the cloud points. This latter work dealt with a crude oil of fixed composition, and the question immediately arises as to the effect of varying the concentration of asphaltic materials on the cloud point. APPARATUS AND PROCEDURE All viscosity measurements were made with a Bendix Ultra-Viscoson. The Bendix Ultra-Viscoson, which consists of a vibrating probe and an electronic computer. measures viscosity by exciting a thin alloy steel blade on the end of a probe by short electrical pulses in damped oscillation at 28 kilocycles. The blade vibrates longitudinally with an amplilude of less than 55 micron or 20 millionths of an inch. Energy to protlucc this excitation is generated in he computer and transferred to the probe through the connecting cable. The oscillating blade is magnetostric-tive, i.e., it is capable of transforming electrical energy to mechanical energy in the ultrasonic range. Ultrasonic waves are produced in the material surrounding the blade by the oscillating motion of the blade causing layers of the material to slip back and forth over one another at a known frequency. The electronic computer calculates the energy required to produce the sliding motion which is in turn proportional to the viscosity of the material. Actual values of viscosity times density (centi-poise X grams/cc) are indicated on the computer and a continuous D-C signal is provided which is fed into a type 153 Electronic Recorder (manufactured by Brown Instruments Div. of Minneapolis-Honeywell Regulator Co.) The liquid sample container was fabricated from a Lucite cylinder and jacketed by a Luicite water bath. Early experiments using glass and steel sample containers were not satisfactory. since the Ultra-Viscoson was apparently affected by the alterzltion of the magnetic fields surrounding the probe by stresses set LIP in the glass and steel as it cooled. The procedure for determining viscosity-temperature curves was relatively simple. The temperature ot the sample was raised sufficiently high to solubilize all paraffin and asphalts present. After heating, the oil sample was immediately transferred

Jan 1, 1957

By George W. Crawford, W. P. Aycock, E. W. Hough

Forty oilfield brines have been examined so far by a polarographic technique new in petroleum engineering called the "tensatnmetric method" by the team of biochemists who perfected its use in their field. Samples of brine were obtained from various oil fields in which the wells were known to be producing fluid from oil productive zones in well-known geologic formations. Most of the reservoirs from which the samples were obtained are believed to have an active water drive under the prevailing conditions of operation. The 40 samples represent brines produced front 16 different formations of various geologic ages. Graphs have been prepared of the data obtained in the testing of each sample, and the distinctive waife-like curves so obtained are characterized by reproducible profiles, called "response curves." Careful comparison of the response curves of salt water coming from different fields producing from the same geologic formation reveals that the curves are similar. The response curves of salt water coming from productive zones of different geologic formations are characteristically different. Preliminary work offers the further hope that response curves of an oilfield brine indigenous to a particular oil-bearing formation and hence representative of a particular geologic environment, such as deposit-ional and all subsequent morphological conditions, may be of value in reservoir engineering in the interpretation of surface and interfacial phenomena. For example, the wettability of the rock matrix and more specifically, the classification of productive oil-bearing strata as hydrophyllic or hydrophobic may be determinable. However, many more brines must be examined and the resulting response curves analyzed in comparison to known causal phenornena before this objective is achieved. INTRODUCTION One of the perennial moot questions in the literature of petroleum engineering is whether the reservoir rock is oil- or water-wet. Possibly an answer to this question could come from a careful examination of oilfield brines. None of the conventional methods of examining brines (chemical analysis, pH and electrical conductivity measurements, and the like) answer the question. Careful analysis of reservoir behavior observed in the exploitation of oil fields, particularly in the application of fluid injection, has been fruitful to the extent that a few reservoirs are believed to be properly classified. Physical chemistry suggests the behavior of reservoir brine and rock may be due to something in the brine in small amount. The ever increasing development and modification of theory in the general field of surface and interfacial chemistry has, and is, contributing to a better understanding of the problem, particularly as theory is verified by data. The work herein reported was begun in 1953 by Hough and Roebuck 1,2 who employed a new form of alternating current polarography, i.e., tensammetry, developed by Breyer, et a13,4 and who studied eight oilfield brines in adapting tensammetry to petroleum engineering needs. THEORY AND DEFINITIONS Tensammetry is a new technique of inquiry into surface phenomena. Specifically, a weak alternating current voltage is superimposed upon the direct current voltage applied to a dropping mercury electrode in contact with an electrolyte containing a small amount of a surfactant. The resultant alternating current can be measured and provides the experimental data for this new area of research. Under the influence of the direct current voltage, polar molecules arrange themselves in a double layer at the electrode. This double layer may be compared to a variable condenser, the capacitance of which is a function of the imposed direct current voltage. The direct current voltage determines the degree of adsorption of the surface active molecule on the electrode. Whenever the molecules are strongly adsorbed on the electrode, the capacitance of the double layer is low and the alternating current through the cell is low. Desorption occurs at some values of the direct current voltage, and at these voltages the capacitance of the double layer is high, resulting in an increase in the alternating current through the cell. The direct current

Jan 1, 1958

By G. W. Form, W. A. Spitzig

The effects of hydrogen and vacuum shtering treatments on the physical and mechanical properties of arc plasma-sprayed tungsten were inuestigated. Temperatures examined ranged from 3000" to 4000°F in vacuum and 2000" to 3000°F in hydrogen for both single and duplex sintering cycles. Densities of 92 pct of theoretical density were obtained when a long-time hydrogen treatment at 2000°Fpreceded sintering in vacuum at 4000°F for 4 hr. This cycle also produced the highest ualues for modulus of rupture and bend angle. The results of this investigation point out the desirability of using a low-temperature long-time hydrogen treatment prior to a high-temperature vacuum sinter for arc plasma-sprayed tungsten. ADVANCES in the development of arc plasma-generating equipment have provided a high-temperature heat source that makes the fabrication of tungsten shapes possible by a metallizing process. Tungsten in the as-sprayed condition is very brittle. It has a density between 80 and 85 pct of theoretical density, a lamellar structure with elongated pores, and a high interstitial impurity content. To improve these properties, sintering treatments can be applied to the as-sprayed material, similar to those used for the densification of compacted tungsten powder. However, in view of the differences in the density and microstructure of as-sprayed tungsten as compared with compacted tungsten, responses to sintering were expected to be different. EXPERIMENTAL PROCEDURES The tungsten powder used in this investigation had a particle size varying from 3 to 13 p with an average diameter of 8p. The impurity level was less than 0.1 pct. The arc plasma spraying was done with an F-40 Thermal Dynamics Corp. plasma jet. Spraying was performed in air and thus required cooling of the substrate by an air blast in order to minimize oxidation. The spraying parameters employed in the fabrication of all specimens are listed below: Power input, kw 12 Arc-gas flow, cfh 95N2 + 5H2 Powder feed rate, g per min 33 Powder carrier gas flow, cfh ION, Spray distance, in. 3 Traverse rate, in. per min 30 Mandrel speed, rpm 100 Nozzle orifice, in. 7/32 These values of the spraying parameters correspond to optimum conditions ascertained in a previous study. Sintering was conducted at 3000°, 3500, and 4000°F in vacuum (< 0.1 Hg), and at 2000 and 3000°F in hydrogen. Duplex sintering treatments investigated are listed in Table I together with the designations that will be used for reference throughout this paper. The samples were fabricated by spraying onto a copper mandrel which was removed prior to sintering. The specimens used for the sintering analyses had the shape of small hollow truncated cones 1 in. high with an inside diameter varying from 0.500 to 0.125 in. and a wall thickness of 1/8 in. Specimens for bend testing were taken from hollow hexagonal prisms 1-1/2 in. high with a 1-in. diam across the flats and a wall thickness of 1/8 in. The bend-test specimens were ground to the dimensions 0.085 by 0.350 by 1-1/2 in. Prior to bend testing 0.0025 in. of stock was removed from each surface by electro-polishing. Density measurements were made by the water-displacement method. In addition, a porosimeter was used to determine the amount of interconnected porosity for representative samples. Strength and ductility were determined from recorded values in transverse bending using a cross head speed of 0.020 in. per min. The load was applied at the midpoint of a 1-in. span. The deflection data reported herein refer only to the plastic portion of the total deflection. RESULTS AND DISCUSSION The as-sprayed samples had a density corresponding to 83 pct (l pct) of the theoretical density of tungsten. Fig. 1 shows a representative as-sprayed tungsten structure.

Jan 1, 1964

By G. S. Cole

The temperature has been measured ahead of stationary solid-liquid interfaces under conditions approximating luzidirectional heat flow and therefore unidirectional solidification. Natural convection flow patterns may be deduced from the temperature distributions , temperature fluctuations, and shape of the interface. Fluid flow increases with the height and the rate of heat transfev through the interface and this is further manifested by a deviation of the interface from aflat vertical plane. The influence of fluid flow on solute inhomogeneity during alloy crystal growth can be inferred from the observed temperature distributions. A buoyancy force exists in the liquid ahead of a vertical solid-liquid interface, caused by a difference in density between cold fluid near the interface and warmer fluid in the bulk liquid. When the viscous and inertia forces in the melt exceed this buoyancy force, a flow of fluid takes place, termed natural or free thermal convection. Natural convection in purely liquid systems has been extensively studied for many years. 1"u On the other hand, fluid flow during horizontal crystal growth has oniy recently been the subject of experimental investigation."-25 The requirements for horizontal crystal growth differ from other heat flow systems. The small aspect ratio (ratio of height of cold wall to length of fluid) has never been considered. The uniform furnace gradient which supplies heat radially (and not necessarily symmetrically) differs from previous boundary conditions of uniform heat flux at the cold and hot ends. And most important of all an isothermal s/l interface is present which can adjust its shape and position to conform to heat and fluid flow. All of these boundary conditions involve complexities which cannot be readily solved analytically. Preliminary observation has demonstrated the penera1 shape of the natural convective flow pattern in transparent media.20&apos;24&apos;25 The flow is circulatory, directed toward the interface at the surface of the liquid, down and away from the interface at the bottom, and then up at the hot end of the melt. During crystal growth such a flow may interact with the solute boundary layer at the s/l interface to affect solute incorporation.M&apos;1B|28&apos;i!T Evidence has also been presented recently to show that thermal convective flow will affect the structure of ca~tin~s.~~-~~ The rate of heat transfer (conduction plus convection) in a given fluid system is a function of the temperature difference between the hot end of the liquid and the s/l interface and the height of the interface. At the lowest values of these variables* all heat is *It has been shown&apos; that adverse temperature gradients as low as O.OOS°C oer cm are sufficient to cause convection. transferred by conduction. When the temperature difference or interface height are increased, laminar fluid flow commences and heat transport takes place by laminar convection as well as by conduction; turbulent heat transfer takes place at higher values of these variables. In the transition region between laminar and turbulent flow, boundary layer separation takes place; fluctuations in temperature are also noted and increase in amplitude and frequency as turbulence becomes dominant. In this paper, fluid flow patterns in the melt ahead of a stationary interface are deduced from observations of temperature distribution and fluctuations, heat flow rate, and interface shape. The fluid flow ahead of advancing interfaces and the effect of such flow on solute incorporation may be inferred from these measurements on stationary interfaces. Observations during enforced fluid motion will also be considered. EXPERIMENTAL PROCEDURE The metal was contained in a lava boat 10 cm in length, 1+ cm in width, and 2 cm in height, as shown in Fig. 1. A water-cooled, molybdenum block heat-sink is at one end of the boat; surrounding this assembly is a slotted stainless-steel tube noninductively wound with a nichrome heating element. Temperature was measured by 38-gage Chrome1 vs Alumel thermocouples sheathed in 0.05-cm-diam graphite-coated stainless-steel tubing, which were moved longitudinally and vertically through the melt by means of a two-dimensional motorized micrometer stage. In some experiments the thermocouple junction was exposed, but in the majority of experiments the junction was welded to the sheath tip; no significant difference

Jan 1, 1968

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By C. R. Johnson, R. A. Greenkorn, R. E. Haring

Three confined five-spot miscible displacements at unity, favorable, and unfavorable mobility ratios were conducted in a shallow, water-saturated sandstone of Pennsylvan-ian age near Chandler, Okla. These studies, plus associated laboratory experiments, were designed to measure miscible displacement performance in a controlled natural system, using known scaling criteria to develop an approach to modeling the heterogeneous field system. We have concluded from these studies that: (I) displacement efficiency in the field is a pronounced function of mobility ratio, indicating that miscible fingering observed in simple laboratory models occurs in the field: (2) field displacements can be quantitatively predicted by scaled laboratory models if the degree and location of field permeability variations are preserved in the models: and (3) arbitrary simplifications of heterogeneity will not necessarily predict observed displacement efficiency, and the simpler the model, the more optimistic the prediction. INTRODUCTION Many processes to achieve miscible displacement of reservoir oil by injected fluids have been conceived and field tested by the oil industry. Among the better known are high-pressure gas, enriched gas, and LPG banks. The simplest form of miscible displacement—one fluid miscibly displacing another fluid of different viscosity but the same density—has been studied extensively in homogeneous laboratory models. Observations of unstable fingering have been made which explain the significant decrease in displacement efficiency as the mobility ratio (ratio of displacing fluid mobility to displaced fluid mobility) increases. General industry experience with field tests of miscible displacement projects, mostly LPG banks, has been premature solvent breakthrough and lower than predicted production rate increases. These results have been attributed to either unstable fingering, unusual or unexpected permeability stratification, or both. Miscible displacement data in a controlled natural system have never been reported, however. Also, it has not been shown that properly designed and constructed laboratory models quantitatively predict field-scale behavior. The purpose of the combined field and laboratory ex- periments reported in this paper is twofold. The first was to measure miscible displacement performance at different mobility ratios in natural rock approaching field size under precise, controlled conditions. The second purpose was to utilize known scaling criteria plus several approaches to heterogeneity to model the field. Comparison of model and actual field results should then determine whether or not the laboratory phenomena (manifested by miscible displacement efficiency) are exhibited in large, natural rock systems. We carried out our program by first locating a shallow, water-saturated reservoir whose rock properties were representative of oil-bearing reservoirs. Detailed reservoir description by core analysis and interference testing showed the field site to be heterogeneous. A sequence of controlled, aqueous-phase miscible displacements was conducted at unity, favorable and unfavorable mobility ratios. A central, confined pattern was used to obtain the displacement data. A laboratory program using sand-packed models was conducted to determine the modeling criteria necessary to simulate field behavior of miscible displacement in a heterogeneous system. SCALING THEORY The detailed derivations and descriptions of the scaling laws that apply to laboratory models of reservoirs are adequately described elsewhere, so the following discussion will be restricted to facets of importance in this study. For a displacement in which one liquid miscibly displaces another, the following dimensionless groups are required to have the same numerical value in the model as in the field: The model also must be geometrically similar to the field, be spatially oriented the same as the field (same dip angle), and have the same initial and boundary conditions as the field (same initial fluid saturations and same injection-production well arrangement). When these conditions are satisfied, the theory predicts that at dny dimensionless time (pore volumes of produced fluids) the dimen-sionless flow potential and dimensionless fluid concentrations will be identical at all dimensionless spatial locations within the model and the field. If this prediction is correct, then the local dimensionless velocities must be identical, thus the instantaneous fraction of displaced fluid produced and the cumulative recovery expressed as fraction of original fluids in place must be identical at all dimensionless times. The theory outlined above has been obtained by either dimensional analysis or inspectional analysis of differential

Jan 1, 1966

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.&apos; Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969