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There were two official representatives of Foreign Governments as guests at the Chicago Meeting. One was Frederick Goransson, managing director of the Saudvikens Steel Works, who represented the Jernkonteret, the Iron and Steel In-stitute of Sweden, and who came to this country especially for our meeting. The other distinguished guest was Commander Toublet, who repre-sented the French Embassy. Commander Toublet delivered a most polished address at the Banquet, dealing with the felicitous relations existing between this country and France for the last 150 years. Com-mander Toublet was accompanied by Mrs. Toublet, who won the hearts of all the ladies present, whose guest she was.

Jan 11, 1919

By Albert J. Phillips

The effect of impurities on the flowsheet in the smelting and refining circuits for copper, lead and zinc is reviewed and the interflow of by-poduct metals from copper, lead and zinc plants is pointed out. The principal points of separation of all impurities in the circuits are indicated and the additional steps added to these circuits in order to effect impurity separation me shown. In this day and age, when difficult metallurgy is mentioned, one thinks of the extraction of more refractory or possibly the alkaline earth or rare-earth metals. It is true that the extraction of metals having a high affinity for oxygen and deleterious solubility for that element in the liquid metal, affords some of the most difficult extractive metallurgy problems. When this is coupled with an affinity for hydrogen, nitrogen, and carbon a devious approach is required that sometimes rivals the complexity of the metallurgy with which this paper deals. However, in all such cases the aim is for a simple

Jan 1, 1962

By R. H. Widmyer, G. M. Wood

This investigation was prompted by the absence of a simple, accurate method to predict optimum second stage separation pressure in three stage separation operations. Three stage separation as used here includes two separators plus the stock tank. The first stage pressure is usually fixed by gas sales conditions and the third stage is at atmospheric pressure. Thus, the second stage pressure is the only one that may be varied in-discriminantly during production operations. No variations in temperature were considered in this study, even though it will vary among systems, for a change in temperature has little effect on the optimum pressure. Optimum pressures may be determined from flash calculations, but these are tedious unless a computer is available. An early attempt to develop a simpler method&apos; yielded an equation which gave the optimum pressure only as a function of initial and final pressure. Experience, however, confirms theoretical relationships which show that composition as well as pressure and temperature must be a factor. This indicates that the basic relationship should be an equation of the form, where P, is second stage pressure, P, is first stage pressure, A is a function of P. (stock-tank pressure) and the system composition, and n is a function of the number of stages and the system composition. Fig. 1 shows the basic variation of P2 with P for a fixed system composition. A series of such figures clearly showed the effect of composition. The peak of each curve reflects that second stage pressure at which the stock-tank recovery (gal/MMcf) residue gas is a maximum value. DEVELOPMENT OF NEW CORRELATION Wellstreams having 17 different analyses, ranging from low gravity crude to condensate, were used to determine the effect of composition. Each wellstream was flashed through three stages to determine the optimum second stage pressure for each first stage pressure. Equilibrium vaporization ratios proposed by Latham and Campbell were used throughout. The heptane plus fraction, for simplicity, was assumed to have the properties of octane. The results were subjected to an empirical analysis in an attempt to develop a correlation- that would be (1) simple, (2) accurate, and (3) eliminate the need for any flash vaporization calculations. This analysis yielded two equations, one for wellstreams having a specific gravity greater than one (air = 1.0) and one for those less than one. For crude streams (specific gravFor condensate (specific gravity < 1.0),

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.&apos;-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.&apos; It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about &apos; 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965

By R. W. Drier

THE conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in property or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology. This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest.

Jan 1, 1929

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&apos;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&apos;, 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&apos;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 David Schroeder, John Chipman

Jan 1, 1964

By Douglas D. Donald

The New Jersey Zinc Co. successfully holed through a 2 1/2-mile haulage tunnel connecting its new Ivanhoe shaft with the Van Mater Shaft at Austinville, Va. This 8x 10-ft cross-section tunnel was driven from both ends and met at a point approximately a mile from one shaft and a mile and a half from the other. In order to make certain that the faces met accurately on line and grade it was necessary to refine conventional mine surveying practices. The mines that are serviced by these shafts are located in the southwestern part of Virginia approximately midway between Roanoke and Bristol at the west foot of the Blue Ridge. While the presence of lead-zinc sulfide ores has been known in this area for more than 200 years, it was in 1902 that New Jersey Zinc Co. acquired the Austinville property, which has been in constant operation since that time. About ten years ago the company undertook an extensive diamond drilling program at Ivanhoe several miles to the southwest. This program was successful in locating sufficient ore to justify the purchase of a number of the properties in this area and plans were made to develop the new orebodies. The discovery of this ore as well as substantial addi- tional reserves at Austinville resulted in a decision by the company to increase its daily milling capacity to 3000 tons, of which about 1000 tons would be supplied from the Ivanhoe mine. After careful consideration of all possible methods of transporting this volume of ore from Ivanhoe to the mill, it became evident that diesel locomotive haulage through a 2½-mile tunnel between the two mines would best suit prevailing conditions. Since the lowest operating level, known as the 1100 level, of each mine would be at approximately the same elevation, it was obvious that such a tunnel should be driven on this level. Not only would this tunnel facilitate feeding Ivanhoe ore into the underground crusher and skip loading installation at Austinville, but it would also open up a known orebody 5000 ft southwest of the Van Mater shaft. In addition it would provide a valuable diamond drilling base from which a large and a potentially favorable but untested block of ground might be explored. In order to hasten the completion of the tunnel, it was felt that it should be driven from both ends. ENGINEERING CONTROL PROCEDURES It was vital that the tunnel junction be made accurately on line and grade; thus it was felt that engineering control of an unusually high degree of reliability was required to prevent an accumulation

Jan 1, 1959

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.&apos; Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

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&apos; and van Everdingen&apos; is well known. Since the publication of their pioneering work, others"&apos; 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&apos; 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&apos; utilized Kelvin&apos;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 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 P. E. Fitzgerald, J. C. Gindlesperger

1. The Acidizer (Trade Publication of Dowell Inc.): No. 1. Aspects of Acidizing. No. 2. Inhibited Acid. No. 3. The Value of Acidizing. No. 4. The Chemistry of Acidizing. No. 5. Jelly Seal in Acidizing. No. 6. Loosening Stuck Drill Pipe. No. 7. The Geology of Acidizing. 2. J. C. Albright: Acid Is Being Used for Cleaning Intake Wells in Water-flooded Areas. Oil Weekly (Sept. 23, 1935) 24. 3. D. H. Bancroft: Acid Tests Increase Production of Zwolle Wells, Miller County, Arkansas. Oil and Gas Jnl. (Dec. 22, 1932) 42. 4. A. H. Bell: Possible Areas for Acid Treatment in Illinois. Pub. of Illinois- Indiana Petr. Assn. and lllinois Geol. Survey (1934) 49. 5. N. A. Best: Treating Limestone Formations Consists of More than Pouring Hydrochloric Acid in the Well. Oil and Gas Jnl. (April 5, 1934) 54. 6. L. G. E. Bignell: Sealing Off Salt Water from Oil-bearing Formations. Oil and Gas Jnl. (Jan. 30, 1936) 59. 7. L. G. E, Bignell: Acidizing Upper Limestone Formation Facilitated by the Use of Jelly Seal. Oil and Gas Jnl. (March 5, 1936) 30. 8. L. G. E. Bignell: Bailing, Shooting, Tubing and Acidizing Have All Been Tried in Deep Test at Binger, Oklahoma. Oil and Gas Jnl. (May 10, 1934) 38. 9. L. G. E. Bignell: Dowel1 Incorporated Increasing Its Field Service for Acid Treatment of Wells. Oil and Gas Jnl. (June 7, 1934) 62. 10. L. C. Chamberlain, Jr. and P. E. Fitzgerald: Oil Well Acidizing in Michigan. Mich. Acad. Sci. Papers (March 1937). 11. M. E. Chapman: Some of the Theoretical and Practical Aspects of the Acid Treatment of Limestone Wells. Oil and Gas Jnl. (Oct. 12, 1933) 10. 12. C. E. Clason and J. G. Staudt: Limestone Reservoir Rocks of Kansas React Favorably to Acid Treatment. Oil and Gas Jnl. (April 25, 1935) 53. 13. W. F. Cloud: Cleaning and Reconditioning Oil Wells—Reconditioning by Use of Acid (Petroleum Production 1937), 389. University of Oklahoma Press, 1937,&apos; 14. K. A. Covell: Developments in Eastern Production Practice. Acid Treatment of Michigan Wells. Amer. Petr. Inst. Prod. Bull. 213 (1934) 77; Oil and Gas Jnl. (May 31, 1934) 89; Oil Weekly (May 28, 1934) 17. 15. B. A. Cunningham: Acid Treatment of Lime Formations. Amer. Petr. Inst. Paper 901 (1933) 9D, 1-7. 16. 0. I. DeSchon: Pondera Production up 22,000 Barrels. Montana Oil & Min. Jnl. (Jan. 26, 1935) 1.

Jan 1, 1937

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 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 Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.&apos; 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,&apos; 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 Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman&apos; equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday&apos;s constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune&apos;s compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25&apos;C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:&apos; where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"&apos; system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

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

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K&apos; = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950