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By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By H. B. Charmbury, D. R. Mitchell

Everyone in the coal industry from top management to the preparation engineer is vitally interterested in recovering as much salable coal as possible from the run-of-mine product. Coal losses from a preparation plant occur in the solid refuse material being discharged from the plant and in the bleed-off slurry from the water circuit. The refuse is generally hauled from the plant in solid form by trucks, conveyors, or aerial trams to the refuse or culm banks or it may be crushed and transported by hydraulic methods to refuse ponds or dams. The loss of coal in refuse material and the extent of this problem has been covered in another paver.' The loss of salable coal in the plant bleed-off slurry is one of the water circuit problems in coal preparation plants. Slurries originate at various places in the processing circuits and are usually disposed of by transportation to waste ponds known as slurry ponds. Even though the combustible material discharged as slurry and refuse from the plant is labeled a loss, the loss must only be considered temporary. There is a tendency at the present time to examine refuse and slurry losses and to reprocess these materials to recover valuable coal. Slurries from eight bituminous coal preparation plants in central and western Pennsylvania have been sampled and examined to determine the amount of recoverable coal in each. Examinations of the samples were made to determine the tons per hour of solids and the gallons per minute of water in the slurry; the size, ash, and sulfur analyses of the solids; and the sink-float characteristics of the larger solids. The extreme fines (—325 mesh material) from one of the samples has been examined further to determine the micron size fractions as well as the ash and sulfur content of the micron sizes. Collection of the Samples: Field trips were made to each of the plants where samples were obtained and discussions held with the preparation engineer prior to sampling. The flowsheet of the plant operation was studied and a time-period selected to obtain a representative sample. At least 20 1-gal samples of total plant bleed-off suspensions were collected at each plant in increments over designated periods belived to be typical of the plant flow Three of the samples were obtained from plants in the Pittsburgh area. Each plant supplied information on the capacity, operating time, type of cleaning equipment used, water and material balances, and auxiliary equipment. From the time required to collect given amounts of slurry and from the amount of solids in the slurry, total solids discharges from the plant were calculated and compared with the plant flow. Ash and sulfur analyses of the total solids were also checked, at some plants, with company figures. In all cases where checks could be made there was reasonable agreement between company figures and those reported here. Analysis of the Slurries: Representative fractions of properly agitated samples were examined in the laboratory to determine the specific gravities of the slurries. The solids and water were separated by filtration to check the weight of each so that the percent of solids in the pulp could be determined. From the resulting data, presented in Table I, it may be seen that the percent solids in the slurries ranges from 2.8 to 39.0 and the amount of solids from 2.61 to 45.61 tph. Size Analysis of Solids: Representative fractions of the slurries were permitted to settle and the clear water was removed by siphoning. The solids were then wet-screened at 28, 35, 48, 65, 100, 150, 200 and 325 mesh. Results of the size analyses are presented in Table 11. These results indicate the extreme variation of sizes and in most cases the degree of fineness of the solids. The amount of —325 mesh ranges from 22.5 to 84.5 pct and the amount of+200 mesh from 8.3 to 69.1 pct.

Jan 1, 1961

By Robert G. Nisle

The classic theory of pressure build-up in shut-in oil wells as developed by Horner and van Everdingen is based on two-dimensional radial symmetry in the well-reservoir system. Such symmetry does not exist in the case of a well which parfiially penetrates the producing formation. As a result of this lack of symmetry the use of the classic theory in such cases become questionable. In this paper the mathematical theory has been extended to include the case of partially penetrating wells. Numerical solutions illustrating the up-dication of the equations are presented. The effect of partial penetration on pressure build-up is shown by a comparison of synthetic pressure build-up curves derived from the numerical solution of the equation for partially penetrating wells for various degrees of penetration. It is shown that partial penetration is detectable from the characteristic shape of the pressure build-up curve and that formation productivity may be calculated from the pressure buildup data in a manner identical to that described by the classic theory. INTRO DUCTION The use of pressure build-up data on shut-in oil wells is a well-established technique for the measurement of reservoir productivity. The work of Homer' and van Everdingen' is well known. Since the publication of their pioneering work, others"' have elaborated and extended the technique. These authors have dealt exclusively with the case of wells that completely penetrate he producing formation. Two-dimensional radial symmetry is achieved, thereby, and the problem is greatly simplified. This ideal situation is seldom encountered in practice. But, in spite of this, the technique is often employed anyway. The question, therefore, arises: how much confidence can be placed in the results of such calculations when the data are taken on wells that only partially penetrate the producing formation? It is the purpose of this work to answer this question. Only the single-phase fluid case will be considered. van Everdigen' has presented a rigorous solution of the two-dimensional case, but because of mathematical complexity, this solution has not proved to be particularly useful. Horner' utilized Kelvin's point source solution in two dimensions and showed that it is a sufficiently good approximation for oil reservoir studies. The geometry of the well and the producing formation is illustrated in Fig. l. Geometrically the formation may be described as an infinite slab. The infinite slab is defined as the solid (the porous medium in this case) bounded by two parallel planes. Thus, the slab extends to very great distances in both the positive and negative directions of two of the coordinate axes, but is finite in

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.&apos; In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.&apos; Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling&apos; the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By David P. Shoemaker, Clara Brink Shoemaker

The I phase was discovered by Bardos, Malik, Spiegel, and Beck1 in the V-Ni-Si system at 1100°C and in the Mn-Co-Si and Mn-Ni-Si systems at 1000°C. Kuzma and Hladyshevskii2 and Kuzma, Hladyshevskii, and cherkashin3 have reported a new phase, which they named the S phase, in the Mn-Co-Si and the Mn-Ni-Si systems at 800°C at approximately the I phase compositions. The powder diffraction diagrams of the I and S phases, compared by Bardos el al.,1 are related but show distinct differences in relative intensities. Professor Paul A. Beck kindly sent us a specimen of the (v-Ni-Si) I phase for single-crystal study. Precession and Weissenberg diagrams taken with a tiny single-crystal fragment showed that the structure is monoclinic with a large unit cell. The cell dimensions were refined from a powder diffraction diagram taken with CrKa radiation in a 57.3-mm camera with our computer program LSCELP4 using only the indices of those reflections that were observed on Weissenberg diagrams (hnl, with n = 0 through 9 and n = 12) and precession diagrams (Okl, lkl, Izk0, hkl, hk2). Table I shows the agreement obtained between the l/d values calculated with the final values for the cell dimensions and the l/d values observed by Bardos et al .1 for I(V42Ni33Si25), by US for I(V41Ni36Si23), and by Kuzma and Hladyshevskii2 for S(MnpCoSi). The powder patterns contain many broad and diffuse lines. In fact practically all powder lines observed are near-superpositions of several reflections. The refinement program is not set up to handle several reflections contributing to one observed line: the position of each line is refined with the aid of one set of indices only. The final values for the cell dimensions were obtained from the lines of strong or medium intensity with the indices indicated by asterisks in Table I: a0 = 13.403(6), bo = 23.336(15), co = 9.129(6)A ß = 99.11(6) deg The standard deviations (given in parentheses) are those calculated by the refinement program from least-squares theory and do not take into account that the lines included in the refinement may not have been correctly indexed in every case or that the position of a line may also be partly determined by the overlapping reflections. The agreement between the calculated and observed I phase patterns is fairly good, although some discrepancies occur. Not all observed lines could be indexed with the incomplete set of sin-

Jan 1, 1968

By S. A. Hovanessian

The method of characteristics which reduces the Buckley-Leverett mnlineur, partial differential equation to two first-order, linear differential equations is applied to the solution of a waterffood recovery problem for multiple lines of producing wells and one line of injection wells. The application of the method is described by a numerical example, and a brief theoretical background is given. From the results of this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple sets of producing wells. INTRODUCTION In this paper, the method of characteristics is applied to the solution of a waterflood recovery problem with multiple lines of producing wells and one line of injection wells. The application of the method to this type of recovery problem considerably simplifies the procedure of obtaining a numerical solution. It differs from the method described by Kern1 because it eliminates the need for integration in obtaining saturation fronts. In addition, the saturation history at any location within the field is obtained from a single diagram (time vs distance with saturation as a parameter)&apos;. The paper includes a brief theory of the method of characteristics and its application to the solution of oil recovery problems. A numerical example is worked out, and the cumulative oil recovery-vs-time curve for a system with multiple sets of producing wells is obtained. This curve is then compared with the recovery curve of a system with only one set of producing wells. From this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple lines of producing wells. However, the recovery time is considerably longer for multiple sets of producing wells.

By A. T. Miesch, L. B. Riley

Distribution of minor elements in sandstone-type uranium deposits of the Colorado Plateau is being studied by the USGS on behalf of the A EC. A primary objective has been to provide basic data which could be useful in geo-chemical exploration for new deposits. The basic statistical measures — similar to those used in sedimentary petrology—are described. The underlying principle is that the frequency distributions fit or approach the log-normal form. Since 1952 the U. S. Geological Survey on behalf of the U. S. Atomic Energy Commission has conducted a study of the distribution of minor elements in sands tone-type uranium deposits of the Colorado Plateau. A primary objective in this study has been to provide basic data which could be useful in geo-chemical exploration for new deposits. Among the basic data considered important are estimates of the abundance and habit of each element in the ore and in the host rocks. It has been found that a few basic statistical techniques, and variations of these techniques, are useful in this type of study. Some of the basic techniques have been used to advantage by researchers in geochemistry and in other fields of geology, especially sedimentary petrology; others have been used to only a limited extent. Among the latter is the linear correlation coefficient, which has proved useful in assessing the element associations in a particular rock type without analysing individual mineral separates. In computing the basic statistical measures a scale has been used which is, in some ways, similar to the phi ($) scale used by sedimentary petrol-ogists in grain-size studies.&apos; FREQUENCY DISTRIBUTIONS It has been recognized for some time that the results of analyses for a given minor element in a suite of samples of rocks or ores yield frequency distribution curves which are approximately normal when the curves are plotted on logarithmic or geometric scales. In other words, the analytical results give an approximate lognormal frequency distribution. A classical example is given by D. G. Krige2 in the study of the distribution of gold values from a mine on the Witwatersrand. Another example is shown in Fig. 1, the distribution of barium concentrations in samples of uranium ore from the Chinle formation. The geochemical data are analogous to grain-size data gathered by the sedimentary petrologist. Both types of data, after simple logarithmic transformations, may be treated by conventional statistical methods based on the normal distribution. This is not to say that other types of transformations may not serve equally well or better for particular element distributions.3 Spectrographers and other analysts are quite aware of the dependence of their precision on the concentration of the element present.4 For example, in the part per million range the variation may

Jan 1, 1961

By David Schroeder, John Chipman

Jan 1, 1964

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By M. Mortada

Nonsteady-state flow of slightly compressible liquids in porous media of non-uniform properties has been the subject of a number of recent studies. Most of these studies considered one-dimensional flow in systems with cylindrical geometry and with the properties of the porous medium varying with radial distance only. A. Houpeurt&apos; studied the problem in its general form by examining the solutions of the differential equation, In Eq. 1, the permeability k and the porosity + are arbitrary functions of radial distance. Houpeurt concluded that, except for special forms of the functions k and the problem is not well suited for mathematical treatment, but lends itself to high-speed digital computation. Carslaw and Jaeger&apos; discussed the solution of Eq. 1 for the case in which the permeability varies as a power of the radial distance. P. Albert3 studied analytically the pseudo steady-state solutions in systems of finite radial extent and non-uniform properties. He also obtained some numerical solutions for nonsteady-state flow using a high-speed computer. William Hurst4 examined the interference pressure drop due to a point sink located in an infinite system consisting of two permeability regions in series. In this case, the permeability changed at a radial distance r from the point sink. INTERFERENCE BETWEEN OIL FIELDS IN A NON-UNIFORM AQUIFER The interference pressure drop for oil fields located in an extensive aquifer of uniform properties is discussed in a number of places in the literature. This work considers the interference pressure drop for oil fields located in a non-uniform extensive aquifer comprising two regions of different properties as shown in Fig. 1. Region I of the aquifer extends from which is the radius of Oil Field A, to ar,,, where a>1. It has permeability k,, porosity +, and effective compressibility c,. Oil Field B is located in Region II which extends from ar, to infinity and has different properties from those of Region I, but the same formation thickness h. Region II has permeability k2, porosity and effective compressibility c2. The choice of this type of aquifer should not imply that it is of frequent occurrence. It is chosen primarily to illustrate the effects of non-uniform aquifer properties on oilfield interference. It is of interest to point out that a non-uniform radial aquifer in which both the permeability and the porosity are inversely proportional to the radial distance can be treated in a manner similar to a linear aquifer of uniform properties. The situation where only the permeability varies as the inverse of the radial distance is also amenable to analytical treatment. Both aquifers behave quite differently from a radial aquifer with uniform properties so far as the water influx and the interference pressure drop are concerned. METHOD OF SOLUTION The expression for the interference pressure drop in Oil Field B due to a constant rate of water influx in Oil Field A is developed in the Appendix. This is accomplished by the simultaneous solution of two partial differential equations describing the pressure in Regions I and 11. The two differential equations are solved subject to the following conditions: (1) at r,, the pressure gradient is constant; (2) at ar the pressure and

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the

By E. P. Abrahamson II

The effect of transition elements which form binary solid solution upon the recrystallization temperature of zirconium has been investigated. All additions raised the recrystallization temperature. A correlation is obtained between the logarithm of the rate of change of recrystallization temperature with atomic percent solute and the free atom ground state electron configuration of the solute element. ThE work of Abrahamson, et al., on dilute binary solid-solution alloys indicated a correlation between the free-atom ground state electron configuration of the solute and either the brittle-ductile transition or recrystallization temperature. These studies were carried out on bcc base materials. The implication is that the outer s and d electrons of the solute are the prime determinant of the absolute rate of change of recrystallization or transition temperature. Furthermore, the limit of linearity has been shown to be a function of solute electron configuration for recrystallization in iron and vanadium. To date no Complete systematic recrystallization study of dilute binary zirconium base alloys has been made. It is the purpose of this study to note whether the change in solvent structure from bcc to hcp will influence the correlation. It was also desired to learn more of the role of the electron configuration of the solvent on recrystallization temperature. PROCEDURE All alloys were made using 99.87 pct Zr with 0.01 Cr, 0.04 Fe, 0.006 Hf, 0.003 Mg, 0.003 Mn, 0.003 N, and 0.080 0 (132 BHN). The solute elements were 99.9 pct pure. According to the published binary phase diagrams6 and metallographic examinations at X750, all alloys used were solid solutions. The alloys were arc melted and remelted six times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot pressed at 950°C to 0.450 in., upset pressed to 0.350 in., and annealed at 800°C for 1 hr. The specimens were then Blanchard ground to 0.250 in., removing 0.050 in. from each side. The grain size of the material at this stage was found to be 8000 100 grains per sq mm. The specimens were then cold rolled to 0.130 in. and cold pressed to 0.125 in., yielding 50 1 pct cold work. All alloys were then chemically analyzed for the principal addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The rolled sheet was cut into 6.75 by 0.25-in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was 250o to 900°C over the 6-in. length, recorded continuously by six thermocouples resting on each specimen. Control was 3oC, accomplished at the hot end. The recrystallization temperature was determined metallographically using polarized light. The criterion chosen was the point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be 3°C. RESULTS Three different pure zirconium specimens were tested, and the recrystallization temperature was

Jan 1, 1962

By R. G. Turner, M. G. Hubbard, A. E. Dukler

Gas phase hydrocarbons produced from underground reservoirs will, in many instances, have liquid phase material associated with them, the presence of which can affect the flowing characteristics of the well. Liquids can come from condensation of hydrocarbon gas (condensate) or from interstitial water in the reservoir matrix. In either case, the higher density liquid phase, being essentially discontinuous, must be transported to the surface by the gas. In the event the gas phase does not provide sufficient transport energy to lift the liquids out of the well, the liquids will accumulate in the wellbore. The accumulation of the liquid will impose an additional back pressure on the formation that can significantly affect the production capacity of the well. In low pressure wells the liquid may completely kill the well; and in the higher pressure wells there can occur a variable degree of slugging or churning of the liquids, which can affect calculations used in routine well tests. Specifically, the calculated bottom-hole pressures used in multirate backpressure tests will be erroneous if the well is not removing liquids on a continuous basis, and gas:liquid ratios observed during such a test may not be correct. Several authors1,3,8,14 have suggested methods to determine if the flow rate of a well is sufficient to remove liquid phase material. Vitter14 and Duggan&apos; proposed that wellhead velocities observed in the field would be adequate for keeping wells unloaded. Jones8 and Dukler3 presented analytical treatments resulting in equations for calculating, from physical properties, the minimum necessary flow rate. An analysis of these studies indicates the existence of two proposed physical models for the removal of gas well liquids: (1) liquid film movement along the walls of the pipe and (2) liquid droplets entrained in the high velocity gas core. Although there probably is a continuous exchange of liquid between the gas core and the film, they will be treated separately for the purposes of this study. The development and comparison of these separate models with experimental data will permit the determination of which, if either, is the controlling mechanism for the removal of liquids from gas wells. The Continuous Film Model Liquid phase accumulation on the walls of a conduit during two-phase gas/liquid flow is inevitable due to the impingement of entrained liquid drops and the condensation of vapors. The movement of the liquid on the wall is therefore of interest in the analysis of liquid removal from gas wells. If the annular liquid film must be moved upward along the walls in order to keep a gas well from loading up, then the minimum gas flow rate necessary to accomplish this is of primary interest. The analysis technique used follows Dukler2 and Hewitt5 and involves describing the profile of the velocity of a liquid film moving upward on the inside of a tube. The minimum rate of gas flow required to move the film upward is then calculated.

Jan 1, 1970

By E. Northcott, F. N. Oberg

By electrostatic separation, course Florida pebble phosphate, too lou-grade to find a ready market, can be upgraded to a satisfactory saleable product. Pebble running from 60 pct bone phosphate of time may be upgraded to 73 to 77 pct BPL depending on the mineralogical. structure of the pebble and the nature of the silica innpurity. High-grade concentrates from Florida pebble phosphate deposits have long been recovered by wet methods. When work was begun in the field, only the coarse pebble (generally +1 mm) was re- covered. In the 1920&apos;s a froth flotation process was developed to separate quartz from the finer phosphate fractions, but this method proved unsatisfactory for treating the intermediate fraction (—1 mm +35 mesh). Consequently various other processes were adapted, including agglomerate tabling and spiral separation of reagentized feed. Today the three processes are used—washing and screening for coarse pebble, tabling or spiraling for intermediate sizes, and flotation for —35 mesh material.

Jan 1, 1959

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum&apos;s work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.&apos; In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors&apos; attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By H. J. Modi, D. W. Fuerstenau

pH effectively regulates the flotation of corundum through its control of the surface charge. Since collector ions function as counter ions in the double layer, the collector must be anionic when corundum is positively charged and cationic when it is negatively charged. Even a long-chained xanthate will float positively charged corundum. Association of the hydrocarbon chains of the adsorbed collector ions gives rise to increased adsorption and increased rate of flotation. Because of this phenomenon, neutral organic molecules aid flotation although the unionized collector cannot promote flotation independently. Na2SO4 was found to depress the flotation of corundum with animic collectors through ionic competition whereas the same salt activates corundum for flotation with cationic collectors. A close connection between ion association, electrokinetic behavior, and floatability is suggested. As part of the increasing interest in the physical chemistry of flotation, strong experimental evidence has been obtained which indicates that organic ions are adsorbed as counter ions by non-metallic oxide minerals mainly because of the electrical forces which exist at interfaces(1-3). Thus flotation of such minerals without activation should then be appreciable only when the mineral and the collector are oppositely charged. Since only limited work has been reported on the effect of surface charge upon flotation behavior(3) this general hypothesis on the flotation of insoluble oxide minerals has not been tested thoroughly. Investigating the flotation of a mineral for which extensive electrokinetic data exist yields a way to test this hypothesis more extensively. The electrokinetic behavior of corundum in solutions containing both organic and inorganic electrolytes has been studied quite thoroughly&apos; Electro-kinetic measurements have shown that in the case of corundum, simply by controlling pH the solid surface can be charged either positively or negatively. For this reason corundum was chosen for study. The object of this paper is to present a study of the flotation of corundum and to explain the results in the light of our knowledge of adsorption mechanisms gained from streaming potential investigations. This paper is concerned mainly with the effect of surface charge on flotation with anionic and cationic collectors, but in addition such flotation phenomena as collector hydrolysis, Van der Waals attraction between hydrocarbon chains, ionic competition, and activation are discussed. While the present paper is confined to a reporting of the data obtained and some of the more immediate conclusions, it will be seen that the results, in combination with those on other systems, do promise a

Jan 1, 1961