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By Lewis M. Haupt

Discussion of the paper of Mr. Granger, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 25, January, 1909, pp. 1 to 37. LEWIS M. HAUPT, Philadelphia, Pa. (communication to the 'Secretary*) :-This subject is of great interest to me, and I am noting progress and conditions as a test of my own judgment in advocating what I believed to be the nearer, cheaper and better route at Nicaraugua. I have as yet learned nothing to change my views, or modify the convictions which led me to retire from the Commission; but that is not the issue to-day. Our government is committed to the Panama route, and is bound to " make good." There are many points presented by Mr. Granger which seem to me worthy of very serious consideration. But when all is said there remains the risk of seismic convulsions, to which either form of canal is subject; and I fail to see that the risk would be reduced by making the cut deeper, with greater surcharge of lateral pressure upon the side walls. A severe earthquake in the rainy season would doubtless close either type of canal. One of the arguments in favor of the Panama route most insisted on, was that Nature had provided good natural harbors at its termini. Recalling this, it has interested me to note that the cost of creating the necessary harbors is estimated at $27,000,000. Mr. Granger refers to this, and quotes the Board's report to the effect that, on the Atlantic side, it will require 5 miles of jetties to " make an excellent harbor out of a wretched one." The vulnerable part of Mr. Granger's paper seems to me to lie in the admission that the plant required is still in the embryonic stage, and that at least one machine should be built and tested " to demonstrate that the theoretical strains and forces work out in practice exactly as expected." This, how-

Jul 1, 1909

By R. C. Neavel

One of the most important requirements to be met by any coal producer is delivery of size consists tailored to specific applications. Generally these specifications include a minimum as well as a maximum size limit. The customers of a major Indiana coal producer noticed that some shipments of sized coal contained a large proportion of undersize pieces. Also, in these shipments, the pieces which remained within the specified limits were cracked and, when handled, crumbled readily. The producer, certain that these shipments had been properly sized at the tipple, suspected that degradation had occurred in transit. The Indiana Geological Survey was requested to examine the coal from one of these shipments to attempt to determine the cause of breakage. Two basic facts about coal and coal seams led to the employment of petrographic techniques in this investigation. First, all coal seams consist of accumulations of diverse organic and inorganic constituents; and second, most coal breakage, either desirable or undesirable, can be attributed to the inherent weakness of some of these constituents or to poor adhesion between certain constituents. Analyses of degraded coal Sampling: Samples were secured from 2 stock piles of 2-by 4-inch coal in a dealer's yard. The coal in both piles had received the same treatment from mining to storage, although it had been mined and shipped on two different days. The size consist of one pile, however, appeared smaller than that of the other. The sample from the degraded pile is referred to as the slack sample, and the other is called the unslack sample. Size analyses: In order to determine the actual size consist, the samples were screened, with a minimum of rough handling, on square 2-inch, 1-inch, 1/2-inch, and 12-mesh screens. It is assumed that 100 percent of the 2-by 4-inch coal is retained on a 2-inch round screen at the tipple. Analyses of several loads at the tipple indicate that approximately 26 percent of the 2- by 4-inch coal, 100 percent of which was assumed held on a 2-inch round screen, passed through a 2-inch square screen. Twenty-six percent may be taken as the normal difference between round and square screens. Results of the analyses of stockpile coal are shown in Table 1. Cumulative percent versus size are plotted on a Rosin-Rammler chart as Figure 1. Both samples approximately follow normal size distribution; this indicates that breakage is not size preferential and also that the samples are representative of the stockpiles. Although both samples exhibit the same general size distribution, the median size of the slack sample is considerably smaller than that of the unslack sample. Fifty-five percent of the unslack sample was undersize (29 percent greater than the normal 26 percent difference), and 83 percent of the slack sample was undersize (57 percent greater than the normal 26 percent difference). Both piles contained a greater percentage than normal of undersize coal; this indicates that they were both affected by degradation, but to a different degree. Bedding-plane analyses: Coal, because of its laminated nature, will break preferentially along bedding planes, especially where adjacent constituents are poorly cemented to each other. Subsequent breakage perpendicular to the

Jan 1, 1961

By David Schroeder, John Chipman

Jan 1, 1964

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 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'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 John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By Rodney L. Stone, David S. Cahn

As part of an over-all laboratory and plant test program to determine mixing ad other techniques for a more economic use of bentonite as an iron ore pellet binder, a settling test for measuring the bentonite content within a pellet or a batch of pellets has been developed. Through this test, it has been shown that dry fracture load is directly proportional to bentonite content in batches of pellets, but inversely propor tional to bentonite content in individual pellets of the same batch. This apparent paradox is explained by a negative correlation between a pellet's size and its bentonite content and the fact that large pellets can withstand a higher fracture load than small pellets. In past attempts to characterize green and dry iron ore pellets, the authors found large variations in the results of strength tests on closely sized pellets from the same batch.' Reasons advanced for such variations in the quality of pellets in which the binder is bentonite were the presence of internal flaws and the nonuniform distribution of the binder. Even when resulting pellet strength is good, there is still the question of whether the same strength could have been attained through a more effective use of a smaller amount of bentonite. The authors' own and other studies 2-3 have pointed out the strong dependence of pellet strength on the degree of "mixedness" of the iron ore concentrate and the bentonite binder. However, before such a relationship could serve as a guide for the development of better mixing techniques and the associated economy of

Jan 1, 1969

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)'. 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 W. A. Krivsky, R. Schuhmann

Jan 1, 1962

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.' 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 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 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 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' 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, I. M. LeBaron

Before describing the electrostatic processing of feldspar, it might be well to review some of the basic definitions and terminology of feldspars. The feldspar minerals constitute a group of alumino-silicates of potassium, sodium, and calcium. Barium feldspar sometimes occurs naturally but is very rare. Hardness varies between 6 and 6.5 and specific gravity between 2.5 and 2.8. Color is generally white or pale shades of red, yellow, or green. The approximate chemical composition of the principal feldspars is given in Table I. The albite (sodium aluminum silicate) and an-

Jan 1, 1959

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' 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

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N's are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,' and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h' + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960

By E. Douglas, D. N. Collins, J. R. Stevens

E. Douglas (Dept. of Scientific and lndustrial Re-search, Warren Spring Laboratory, Hertfordshire, England) — The authors are to be congratulated on the considerable improvements they have made in tailoring efficiency and selectivity terms which are generally superior to the alternative forms in current use. However, I feel that their efficiency expression is limited to lower-grade feeds; its accuracy reduces as the feed grade increases. For example, its application to such processes as the beneficiation of glass sands, refractories and clays will invoIve considerable inaccuracies. The reason for this lies in the direct use of recovery, which, with high-grade feeds, biases their empirical expression, R(1 - c/h). With a 90% grade feed, the recovery weighting for the slightest degree of beneficiation, over a zero efficiency sampling operation, will be 90+%+ I disagree with their second basic requirement which states that there can be no fundamental basis for any single quantifying expression. A formula giving a comprehensive representation of concentra- tion efficiency can be derived fundamentally accord-to the procedure outlined in the literature. '' This formula, called the Basic Efficiency formula, is

Jan 1, 1963

By E. B. Brauer, W. Hurst, J. D. Clark

Because of drilling, completion, and workover practices, the permeability around a wellbore generally is different from the permeability of the formation. The zone with the altered permeability is called "skin" and its effect on the pressure or flow behavior of the well is called "skin effect". Hawkinsl has shown that the radius and the permeability of this zone are related to the skin by: If the permeability in the skin zone is less than that of the formation, the skin is positive; if it is more than that of the formation, the skin is negative. If the two permeabilities are equal, s is zero; that is, there is no skin. Van Everdingen2 and Hurst3 have given mathematical solutions to the case of a zone of reduced permeability around the wellbore. This skin effect is illustrated in Fig. 1. They treat the positive skin as a zone of reduced permeability of infinitesimal thickness around the wellbore. When applied to a well with negative skin, however, their solutions lead to the calculated flowing well pressure which is smaller than the formation pressure, i.e., an injection situation. This is a physical contradiction. In this paper, it is shown that this mathematical difficulty can be overcome by assuming an effective wellbore radius larger than the actual wellbore. Existing solutions2"4 are modified to include the effect of an enlarged wellbore radius, and thus enable the engineer to deal with negative as well as positive skins. Theoretical Development Van Everdingen and Hurst,4 through the use of Laplace transformation, obtained the following expression for transient fluid influx into a wellbore: The values for QtD, reported extensively by van Everdingen and Hurst,4 are obtained from the following integral:

Jan 1, 1970