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By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By W. R. Webb, M. O. Peterson

WHEN men drive haulage equipment ranging up to 22 tons in an open pit operation, they must live with the realization that their safety is dependent upon the machines they drive and how well they operate them. The hazards inherent in their jobs must be recognized, met, and defeated. It comprises a never ending struggle toward perfection-an almost un- obtainable goal. The Jones & Laughlin Benson Mines, at Adirondack State Park in New York, created a safety program which resulted in only one three day lost time accident from April 1948 to April 1952. At the very start of the program, management of the open-pit operation recognized the hazards existing at Benson. The program was designed to meet each danger. With a knowledge of the problem faced, the process of minimizing each facet was planned along lines of maintenance of equipment and training of personnel. Its success is evident. In the ever-present struggle, care and maintenance of machines and application of experience to new equipment design are mainstays. Truck Haulage Benson produced 2.9 million tons of crude iron ore and 1.6 million tons of waste in 1951. To do the job, truck mileage reached 500,000 miles. The tremendous mileage emphasized to safety planners, the fact that the more work done, the greater the possibility of risk in haulage operations. Instrumenting the aim of the safest equipment possible is a methodical servicing program. Like other segments of the drive, the servicing program is based on greater production with fewer accidents. Every truck is serviced at least once per eight-hr shift. Examination includes inspecting and tightening wheel studs, checking tires, steering apparatus, lights, brakes, wipers, heaters, fire extinguishers, and refueling. A running history of the equipment's operating life is kept in the form of service and maintenance records. Machine operators are constantly on the alert for malfunctioning of units. At the first sign of trouble the truck is returned to the garage for exchange. No truck functioning incorrectly is kept on the line, regardless of its shift check schedule. The program resulted in a reduction of the number of costly overhauls and cut down the number of haulage accidents. Miscellaneous Mobile Equipment Auxiliary units, operating within the pit, have presented definite safety problems. The highest accident rate in the pit occurred on trucks carrying water and bits to the churn mills. The weight and awkwardness of bits and drill stems, combined with remote delivery points were direct causes of numerous accidents. Here, the problem has been one of equipment handling, rather than haulage. All air compressors for secondary drilling are truck mounted, facilitating mobility. In addition to making it easier to move the equipment, truck mounting has eliminated many of the hazards connected with relocating machinery. By making air compressors independent of other units, drilling operations have been speeded up considerably. Unseen rocks in the path of moving vehicles are a constant source of tire damage. At Benson the problem has been met by supplying each loading crew with a bulldozer for cleanup operations. The pitman directs the dozer operation, and when truck drivers back into loading areas, he serves as an extra set of eyes. Modern Truck Garage Provides Drive-Through Service Simplicity is the essence of any preventative maintenance program. At Benson, a modern garage, with a drive-through service bay simplifies servicing. Shift inspection of the 22-ton haulage units is accomplished with minimum delay and maximum thoroughness. Major repair work and periodic overhauls are done in the repair section of the truck garage. Crane facilities for handling heavy assemblies ease the job and add to the safety factor. Other mobile machinery,

Jan 1, 1952

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By Rex W. Woods

The clue history of performance of a highly volatile type oil reservoir which is now greater than 80 per cent depleted is presented. The reservoir is at a depth of approximately 8,200 ft and includes an area greater than 7,500 acres. The reservoir has been exploited by 10 wells which to date have yielded about 10,880,000 bbl of stock tank oil by pressure depletion. Reservoir pressure has declined from an original of 5,000 psi to approximately 1,450 psi. Produced gas/oil ratio has increased from 3,200 to 23,000 cu ft/bbl with a corresponriing increase in APl gravity of the stock tank oil from 440 to 620 . Pressure and fluid data are given for different stages of depletion. INTRODUCTION In papers by Sloan,' and Cook, Spencer and Bo-browski,' properties of highly volatile type reservoir oil were discussed in detail and methods were presented for predicting performance of reservoirs containing this type of fluid. The purpose of this paper is to present performance history of a highly volatile type oil reservoir designated as Reservoir A which has been produced by pressure depletion and field separation without processing of gas GEOLOGY The reterence field which includes Reservoir A is a structural feature north of a trend of major folding along a northeast-southwest axis. In the area of development, the structure has the appearance of a dome with formation dip of three to four degrees, but structural relations between the reference field and the axis of major folding to the south have not been determined. No faulting within the field is evident. Oil and gas productive sands have been found at depths of 7,000 ft to 10,000 ft in a columnar section of Mio-Oligocene age. The sand bodies in the section are lenticular and usually continuity of sand is limited to a small area. Sand A which forms Reservoir A at a depth of 8,200 ft, however, has exceptional continuous development in the reference field. Fig. 1 shows an isopachous map of net oil sand for Reservoir A. Net thickness of oil sand at producing wells ranges from 14 to 34 ft with an average of 22 ft. Pinch-out of sand has been shown by drilling in the southwest part of the field, but extent of the reservoir on the northwest and northeast parts of the field is indicated only by thinning of the sand. The vertical oil column between the highest and lowest producing well in the reservoir is 339 ft. No water-oil contact has been found within the reservoir. As interpreted from the isopachous map, the reservoir includes about 8,900 acres with an average net sand thickness of 12 ft. Because of limited data on extent of the reservoir, the isopachous map permits only an approximation of sand volume in the reservoir. DEVELOPMENT AND PRODUCTION Reservoir A was discovered during 1938 and was developed with eight wells to the end of 1942. One well was completed during 1946 and the tenth well in the reservoir was completed during 1951. Three of the original wells and the last completion have produced from Sand A only. Six wells have produced from Sand A through the casing side of dual completions. Initial producing rates of the original wells ranged from 800 to 1,000 BOPD. Production history for the reservoir is shown in Fig. 2. Production of the reservoir was begun during 1940 and in May, 1952, peak production from seven wells was 5,300 BOPD. At the end of March, 1954. cumulative production was 10.880,000

Jan 1, 1956

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 David Cornell

Back pressure test data on natural gas wells are short time test data of unsteady state nature. Performance curves from which unsteady state effects have been eliminated, called stabilized performance curves, are necessary for understanding the behavior of gas wells and for scheduling gas fields for periods up to 20 years. A calculation procedure has been developed whereby three day, seven day, 30 day, or other duration stabilized performance curves may be calculated from back pressure test data. Such curves are essential for correct gas deliverability calculations and gas field scheduling. I NTRODUCTION The manner in which a back pressure test is made will affect the slope of the back pressure curve because the radius of drainage changes with the length of time that the well is allowed to flow. The reciprocal of the slope of the back pressure curve is defined as n in Equation 1 and varies from 0.5 to 1.0. If the flow is viscous and the radius of drainage constant, n will have a value of 1.0. Because of turbulence in the formation near the wellbore, the pressure drop is usually greater than the viscous flow pressure drop and the exponent n is frequently less than 1.0. In addition, since the radius of drainage moves away from the well-bore during the test, the gas flows a greater and greater distance as the test proceeds, with a resulting increased pressure drop at the high flow rates, and, again, n for the test tends to be less than 1.O. The effect of the changes in the radius of drainage may be calculated and the results used in preparing stabilized performance curves for fixed values of the radius of drainage. Such curves can be made for a defi- nite time period, such as three day, seven day, or 30 day stabilized performance curves. These cukes will show the effect of turbulence near the wellbore and can be used to predict the performance of the gas well at any flow rate or for any production period. In order to discuss the importance of the radius of drainage quantitatively, it should be defined. Muskat" defines the radius of drainage as follows: "... the radius of drainage gives the distance from the well to which the approximately steady state condition has been established ... it being assumed that no gas is removed from any point until the radius of drainage has passed that uoint." An eauivalent definition of the radius of drainage is that radius at which the extrapolated portion of the steady state portion of the pressure gradient gives a pressure equal to the shut-in reservoir pressure. This definition is also implied in the back pressure equation. The radius of drainage is, then, the distance into the reservoir from which the gas appears to originate at any time. It is, however, only a useful concept and does not actually exist. Fig. 1 illustrates the definition of the radius of drainage. At the end of each flow period the radius of drainage may depend on three factors: (1) the duration of each flow period; (2) the rate of gas production; and (3) the rate and duration of the previous flow periods. In general, back pressure tests are conducted with various lengths of production time and at various flow rates. Each individual back pressure test, therefore, requires an individual analysis. The calculations of the change in the radius of drainage have been made, however, for the case of equal flow periods for all four production rates and several sets of increasing flow rates. Fig. 2 illustrates the results of such calculations made by the method of Cornell and Katz2 for the case of 8, = 50,000 and the flow rate increasing in the ratio 1.0:2.0:3.0:4.0 for each flow period. The increase in the radius of drainage during the test is apparent.

Jan 1, 1956

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow' and frontal advance' equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas' reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water 'front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,' one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper' for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.' The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. Hartsell Cash

INTRODUCTION Created in 1944 to help rebuild those economies, principally in Europe, which were seriously damaged or destroyed during the Second World War, the World Bank--or to use its correct name, the International Bank for Reconstruction and Development-began its operational phase by making a loan to the Government of France to accomplish two tasks: (i) to import coal for space heating purposes; and (ii) to buy new machinery and equipment to help rehabilitate its coal mines. Once the thrust of reconstruction in postwar Europe was largely accomplished, the World Bank Group (for today the World Bank has three separate lending windows) turned to mobilizing funds to improve living standards in developing countries, which remains its primary goal today. Over this period of time, the World Bank Group has continued to assist the world mining industry in various ways and, since 1955 the World Bank Group has financed mining or mineral processing projects with loans/credits totalling $1.5 billion. The World Bank Group consists of two institutions--the World Bank itself and the International Finance Corporation (IFC), which was founded as a separate institution in 1956 and three separate lending windows--the World Bank, the International Development Association (IDA), and IFC. The World Bank loans are provided at commercially-related interest rates but have grace periods usually of up to 3 to 5 years and repayment periods ranging from around 15 to 20 years. Since the World Bank raises its operating funds on the international capital markets in varying currencies and in varying interest rates, it relends a basket of currencies at floating interest rates which are fixed every six months to reflect the Bank's own borrowing cost. At the present time, the interest rate is just below 10% per year and in addition, a one-time front-end fee of 1/4 of 1% is charged. Also, a commitment fee of 3/4% per year is charged on the undisbursed amount of the loan itself. For loans to industrial and mining projects, it is normal to charge an additional guarantee fee of 1 to 1.5% in addition to the annual interest rate. This guarantee fee is payable to the government of the country in which the project is carried out since, by its charter, the World Bank is required to have the guarantee of the host government for each loan made in a specific country. By far the greatest source of lending funds within the World Bank Group is that of the World Bank itself and for the fiscal year ending June 30, 1984, the World Bank approved loans totalling $12 billion. The second lending window within the World Bank Group is IDA which performs the same functions as the Bank itself and has the same staff. Nevertheless, its loans (called credits) are made on much softer terms and are made to the poorest nations only. IDA funds are subscribed by the wealthier countries, usually as grants, and these are relent as credits to those countries with the lowest per capita income. IDA credits are made for 50 year periods, including 10 years of grace, to the government itself. The credits are interest free, but there is a service charge of 3/4% per year on the amount withdrawn and outstanding to defray the administrative costs of IDA. Credits approved during fiscal 1984 totalled $3.5 billion. The third lending window is IFC. While IFC is a separate corporation and operates quite separately from the World Bank and has its own staff and regulations, it works very closely with the World Bank on its overall approach to the mining sector and to a particular country. IFC's mission is essentially to supply venture capital and to stimulate development of the local private sector in capital markets as well as to promote the international flow of private capital to developing countries. Unlike the World Bank and IDA, the IFC does not lend directly to governments

Jan 1, 1985

By F. W. Jessen, C. A. Johnson

The effect of treatment with ferrochrome lignosul-fonate on both sodium and calcium bentonites has been examined. In the early stages of treatment it appears that some base exchange of iron and chromium for sodium may occur with the sodium bentonite. Such exchange appears specific for exchange of sodium ions when the calcium ion concentration represents 40-5.5 per cent of the total exchangeable cations, and when additions of lignosulfonate are less than 1 lb per bbl. Adsorption appears entirely physical above 1 lb per bbl treatment level for all concentrations of calcium studied. Gel strength and plastic viscosity of both calcium and sodium bentonite systems were reduced with treatments of ferrochrome lignosulfonate up to 2 Ib per bbl, the greatest reduction occurring within a range of calcium concentration of 40-5.5 per cent of the total exchange capacity of the clay. INTRODUCTION The problem of control of viscosity and gel strength of drilling fluids by the action of thinners or dispersants has been studied by many investigators.1-7 In addition, much work has been done on formation of gel structure in clay suspensions. However, gel formation and structure still are incompletely understood, and the use of the various dispersing chemicals is based, to a large extent, on data almost entirely empirical in nature. In recent years the lignosulfonates have become increasingly important in the treatment and control of drilling fluids. More specifically, ferrochrome lignosulfonate has found rather wide acceptance, particularly in calcium systems.5-7 Lignosulfonates are refined lignin products made from spent sulfite liquor from which the fermentable sugars have been removed.15 The exact structure of lignin is not known; however, it is believed to be a phenolic propane type polymer which may exist as a branched chain or cross linked structure. The molecular weights of lignosulfonates probably range from 300 to 100,000 or more.15 A better understanding of the mechanism of adsorption of dispersants is essential before improvement and development of characteristics of drilling fluids and drilling fluid control is possible. This investigation was undertaken to determine the action of ferrochrome lignosulfonate on sodium and calcium montmOrillonite' LABORATORY INVESTIGATION A Stormer viscosimeter and Fann V-G meter were used to measure viscosity and gel strength. A Zeiss spectrophotometer was used for analysis of Fe and Cr and the flame attachment was employed in the analysis of Na, Ca and Mg. A General Electric X-ray diffraction unit utilizing Copper Ka radiation and a Ni-filter was utilized in the X-ray studies. PROCEDURE Two systems were studied. Predominately sodium clay, obtained from Wyoming, and a predominately calcium clay from Texas were used. These particular samples were chosen because of the extensive work of characterization completed by Mungan. Ionic base exchange capacity determined by flame photometry and total exchange capacity by the Kjehldahl method were obtained experimentally. A 7-per cent suspension of the sodium clay and a 20-per cent suspension of the calcium clay in distilled water were prepared by mixing with a high-speed mixer. The suspensions were allowed to stand for two weeks for complete hydration. Calcium chloride was added to portions of the sodium and calcium cla suspensions to obtain suspensions varying in Ca++ concentration as shown in Table I. A series of treatments was run with 500-ml portions of the original suspensions using a ferrochrome lignosulfonate. Treatment was carried out in the same way with each of the suspensions of varying Ca concentration. Viscosity and gel strength were measured and a filtrate obtained at each treatment level. Ten ml of filtrate were diluted to 50 ml, and aliquot portions of the 50 ml were taken for the Na, Ca, and Mg analysis by the flame photometer. The pH of these filtrates ranged from 7 to 7.3. Standard

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949' but

Jan 1, 1952

By R. F. Blakely, P. E. Potter

Any stratigraphic section or bedding sequence can be synthesized if there is a transition procedure from one lithology or bedding type to another, and if thickness distributions of the different lithologies are known. Stratigraphic sections of a fluvial sandstone body were synthesized with five bedding types: cross-bedding, massive beds, parting lineation, ripple mark and mudstone. The transition procedure from one bedding type to another used dependent, Markovian random processes which have a memory that extends one step backward in the depositional process. As observed in nature, median grain size and sand wave thickness (cross-bedding and ripple mark) decline upward in the synthesized sections as proportions of the different bedding types change. Grain size and permeability were also incorporated into the sections. By changing the transition procedures, bed thickness distributions, rate of upward decline or sand wave height and length, different types of sections can be synthesized, thus making it possible to model many different sedimentation problems. INTRODUCTION This paper describes a general method for synthesizing stratigraphic sections and bedding sequences of sedimentary, metamorphic or igneous origin. Synthetic generation is of interest for several reasons. Close correspondence between real and synthetic sections suggests that the factors used in the synthesizing model may indeed be the correct ones, thus giving the investigator a check on his assumptions. Rapid, inexpensive simulation of many stratigraphic sections permits one to synthesize a rock body (sandstone or carbonate reservoir) or, on a larger scale, the fill of a sedimentary basin. Harbaughl gives an example of mathematical simulation of a carbonate basin. He simulated the basin in the hope that improved prediction would follow better understanding of the depositional processes. From the petroleum engineer's viewpoint it seems reasonable to believe that the synthetic generation of rock properties and their distribution in a reservoir should be relevant in the study of reservoirs. Any stratigraphic section or bedding sequence can be generated provided there is a transition procedure from one lithology or bedding type to another, and provided the thickness distributions of the different units are known. The transition procedure involves random processes that are either independent or dependent. If the depositional process is independent, previous deposition will have no influence on present deposition. However, if it is dependent, past deposition will influence either present or future deposition. Such a dependent depositional process can be thought of as having a memory that extends backward in time through one or more pulses of deposition. A process with a memory can be described by a Markov process. Because the concept of memory or dependence appears to be in accord with our understanding of many depositional processes, Markov processes were used to synthesize the bedding sequences of this study (see Appendix). The above methods are perfectly general and are appropriate for any stratigraphic section or bedding sequence: bedding types in a beach deposit, an evolving carbonate bank or the changing lithologic fill of a thick geosyncline sequence. We chose to synthesize a vertical profile of a fluvial sandstone body because its characteristics were well documented, much was known about fluvial processes and fluvial-deltaic sandstone bodies constitute an important class of petroleum reservoirs. CHARACTERISTICS AND ORIGIN OF FLUVIAL CYCLE The fluvial cycle has been well documented in recent years by Bersier,2 Allen3-5and Visher.6,7 Deposits from fluvial cycles range from 10 to 150 ft or more in thickness and are characterized by a "fining upwards": coarse sandstones with occasional conglomerates grade upward into medium- to fine-grained sandstone, and hence into siltstone and mudstone. The dominant sedimentary structure is inclined bedding: thick cross-beds in the lower half

By Robert M. Lewis

Can wet-ground mica be produced from mica schist ores, and if so, would its properties be comparable with products now on the market? This was the problem which prompted the development of a flowsheet for the beneficiation of mica schist. The fine-ground mica industry relies on weathered pegmatites and alaskite ores as sources of raw material. The mica concentrates obtained from these ores are relatively clean and require moderate beneficiation to meet color and bulk-density specifications. Mica obtained from mica schist is iron-stained and decrepitated and requires additional beneficiation to produce a wet-ground mica product. Despite these adversities, there are several advantages to be gained by mining and processing mica schist ores. The mica content of these ores is considerably higher than that of the pegmatites and alaskite ores now being mined, often containing in excess of 40% mica. This higher-grade mica feed should promote a lower mining and milling cost. The mica schist ores with their higher mica content would mean less tailings to handle; however, there would have to be a means for disposing of acid and sulfate wastes. A flowsheet was developed whereby mica could be recovered from mica schist ores and beneficiated in a way that would result in a high-quality end product.' The essential phase of the process involves using reducing reagents to increase the magnetic susceptibility of iron contaminants which then can be removed with a magnetic separator. General Treatment Procedure The mica is floated by either of two methods, an amine float in an acid circuit' or the U.S. Bureau of Mines (USBM) amine-fatty acid float in an alkaline circuit' The flotation mica is ground in a pebble mill to liberate contaminated particles and expose iron-stained surfaces. The concentrate is then conditioned with a reducing reagent and passed through a Frantz Ferrofilter for the removal of magnetic material. The nonmagnetic product is acid-leached to further reduce the iron contamination. The leached material is then ground to product size and checked for specifications. Discussion of Flowsheet and Its Development Flotation: The mica is concentrated by flotation using either of two methods: an amine float in an acid circuit, or the USBM amine-fatty acid float in an alkaline circuit.' The writer does not wish to elaborate on the relative merits of the two flotation procedures; however, after investigating ores from various localities, it was felt that the amine float in an acid circuit was more consistent when using a standard procedure. Iron Reduction and Magnetic Separation: This phase of the flowsheet may be considered the key to the process. It was developed when it became apparent that hot acid leaching had just about reached its maximum effective¬ness for color improvement. S. C. Sun and William Hirsh in "Hydrochloric Acid Leaching of Iron From Pennsylvania Aluminous Clays,"` reported iron extraction for -20-mesh minerals of 82.20% for hematite and only 33.46% for magnetite. The test procedure employs a 19% hydrochloric acid solution, 104°C temperature, and 10% solids. It was felt that magnetic removal of some of the iron contaminants before leaching therefore would be advantageous. Since the iron minerals present as contaminants vary in magnetic susceptibility, it was decided to experiment with reducing reagents as a means of influencing their magnetic properties. Zinc hydrosulfite or sodium hydrosulfite were the reagents used throughout the tests. The procedure developed consists of conditioning the mica concentrate in a closed container at approximately 5% solids with a reducing reagent. Approximately 10.0 lb of zinc hydrosulfite per ton of mica concentrate is used. The ferric iron is reduced to the ferrous state (magnetic) and oxidation is retarded by isolation from the atmosphere in a closed container. After the desired conditioning time has elapsed, the material is passed through a Frantz Ferrofilter where the magnetic particles are retained and discarded as

Jan 1, 1972

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By Goldye Leeds, Marian Balicki

A SURVEY of literature reveals the scarcity of experimental evidence relating to work hardening and reannealing of silver.'-'" With the exception of the well-known X-ray investigation of silver and other metals by W. A. Wood? the effect of progressive cold working has not been studied. The determination of thermal stability of silver in the work-hardened state by means of isochronal or isothermal annealing has been confined apparently to very high reductions only. In the survey made, no study was encountered which endeavored to produce a complete picture of the changes in various properties due to cold working and subsequent reannealing. To fill these gaps and to assemble data that could be used for the determination of activation energies and of frequency coefficients of primary recrystallization, a systematic experimental approach, which was developed by one of the authors, has been applied to pure silver. Material and Processing The silver used was Handy and Harman fine silver, with a spectroscopic analysis at the testing stage of Cu, 0.0001 to 0.001 pct; Te, 0.0001; Pb, Si, Ca, Mg, and Mn, traces. The material was supplied in the form of a rod 0.406 in. diam and was converted into test samples according to the procedure condensed in Table I. It should be mentioned that air annealing was adopted to simulate industrial practice, though it was realized that annealing in a neutral gas or in a vacuum would be preferred. The usual precautions have been taken to eliminate any structural changes and property changes resulting from the storage of the samples prior to annealing or testing. Thus the wires were kept at the fully annealed stage, and the final wire drawing, which produced the desired degree of work hardening, was done just prior to the final annealing or testing. During the short waiting period, the samples were kept in a thermosflask filled with ice. Even with these precautions some strain-age-hardening or self-annealing could occur. To test such a possibility, wires of different reductions were prepared in the manner adopted and portions of them were immediately tested. The remaining portions were similiarly tested after different periods of storage, both at room and melting-ice temperature. Within experimental error, all samples obtained from a wire of a given percentage of reduction yielded identical values. This result qualified the material for further tests and interpretations, because it showed that either strain-age-hardening and self-annealing were absent, or that these effects fully balanced each other. The final annealing was carried out in an electric resistance furnace automatically controlled to within a 10°F. It was realized that the temperature fluctuations were greater than desired for this type of work. TO diminish the errors due to fluctuations of temperature, the hot junction of the thermocouple was placed as close to the samples as possible; the time of soaking was reduced to 15 min; and the number of samples annealed at different temperatures was increased. It will be seen from Table I that some tests were performed on the same material at rising temperature. These will be discussed elsewhere. Room temperature testing was limited to the determination of some of the mechanical properties that are known to be additive in a degree sufficient to be used for indirect study of the kinetics of the reannealing process, Tensile tests, carried out on a manually operated J. Camillon machine, accurate to within permitted the determination of the ultimate stress (U.S.1 and of the 2 in. elongation, (A,). The proof stress (d,e) has been determined from a series of bend tests carried out on a Tinius Olsen Stiffness Tester by using the offset method. This involved accurate determination for each sample of load-angular deflection curves, finding a

Jan 1, 1952