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By Leo B. Bicher, Donald L. Katz

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By J. S. Aronofsky

The results of polentiometric model studies and numerical computations are described. The purpose of these studies was to determine the influence of the mobility ratio on flooding efficiencies during water encroachment in petroleum reservoirs, in systems of regular well geometry. The direct line drive well pattern having relative spacing distances of one and one-half to one was investigated for water to oil mobility ratios of 10. 1. and 0.1. The results of these studies indicate that the pattern Sweep efficiency i.; very dependent upon the mobility ratio. INTRODUCTION The almost universal occurrence of water in the immediate neighborhood of oil-hearing sands lends considerable emphasis to the desirability of having a rational analysis of water encroachment into petroleum reservoirs. This problem has 1)become increasingly important with the accelerated use of water injection for secondary recovery operations. The water encroachment problem has been studied from both the theoretical and experimental viewpoints by Muskat.' He has formulated, in a precise manner, differential equations to express flow in a water encroachment system, and rigorous analytical solutions have been developed for the linear, radial, and spherical cases.' However, it becomes exceedingly difficult to solve the encroachment problem rigorously for any general two-dimensional system in which the shape of the two-fluid interface is not immediately evident from the geometry of the system. The difficulty lies in the fart that a rigorous analytical solution requires that the shape of the two-fluid interface be known simultaneously with its instantaneous posititon and with the pressure distribution on both sides of the interface. Although this paper concerns the study of the two-fluid system of oil and water. the methods described in the paper are generally applicable to other systems of incompressible and immiscible fluids in which the displacing fluid sweep-the displaced fluid down to a residual value. In each region it is assumed there is only one mobile fluid and its mobility is constant throughout the region. The Same procedure. with minor alteration, is applicable for gas injection systems provided the assumption can be made that both the displaced and displacing gases can be described by steady state formulas. For the particular two-fluid problem considered in this paper, there is a relative permeability. K, and a viscosity. p. associated with the water zone, and a different permeability and viscosity associated with the oil zone. The K/p (mobility value associated with a particular volume element of the porous medium. at any instant of time. will depend upon whether the element is ahead of. or behind the advancing interface. It is assumed that all volume elements ahead of the interface are characterized by the K/p value for oil, while all the elements behind the interface are characterized by the K/p value for water. That is. the K/p value in the oil zone is constant throughout the oil zone. and the K/p value in the water zone is also constant but different from the value in the oil zone. The symbols are defined at the end of the paper. The well pattern chosen for initial study is the direct line drive; the swept-out area at breakthrough was determined by two different methods which are described in the section on theory. These are: 1. Potentiometric analyzer 2. Numerical computation The use of the potentiometric analyzer for studying water flooding problems is adequately described in the literature, particularly for cases where the mobility in the water zone is assumed equal to the mobility in the oil zone." ' 5

Jan 1, 1952

According to published reports, controlled production from the Masjid-i-Sulaiman and Haft Kel fields for the year 1934 was as follows: No new development of major importance in either of these areas is reported. Owing to the increasing- demand in North Iran, particularly for gasoline and kerosene, it has been arranged that this market shall in future draw its supplies from a newly constructed refinery at Kennan-shah. This refinery is connected by a 3-in. pipe line, 145 miles long, with the Naft-i-Shah field, on the borders of Iraq and Iran. The crude oil will pass through a topping plant at the field and the products will be stored and pumped to the Kermanshah refinery in such proportions and quantities as are demanded by actual market requirements.

Jan 1, 1935

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

[PAGE PREFACE. A. B. PARSONS 3 OFFICERS AND DIRECTORS 7 STANDING AND SPECIAL COMMITTEES 8 PROCEEDINGS OF 1935 MEETINGS 10 NEW YORK, FEBRUARY 10 CHICAGO, OCTOBER 14 SAN FRANCISCO, OCTOBER 14 HOUSTON, OCTOBER 15 ST. LOUIS, OCTOBER 15 ABSTRACTS OF PAPERS PUBLISHED IN 1935 17 TECHNICAL PUBLICATIONS AND CONTRIBUTIONS, 1935 64 INDEX OF 1935 PUBLICATIONS 71]

Jan 1, 1936

[YEAR OF ELECTION 1913. FRANK DAWSON ADAMS Montreal, Canada 1938. HENRY CORT HAROLD CARPENTER London, England 1933. KARL EILERS New York, N. Y. 1922. FEDERICO GIOLITTI Torino, Italy 1906. SIR ROBERT A. HADFIELD London, England 1921. FRANK WILLIAM HARBORD London, England 1917. HERBERT HOOVER York, N. Y. 1939. HENRY KRUMB New York, N.' Y. 1921. C. McDERMID London, England 1913. EZEQUIEL ORDONEZ Mexico City, Mexico 1935. ROBERT PEELE New York, N. Y. 1938. A. M. PORTEVIN Paris, France 1937. JOHN V. W. REYNDERS New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T. A. RICKARD Victoria, B.C., Canada]

Jan 1, 1940

By R. D. MacDonald, John Dasher, A. M. Gaudin

ION exchange is a widely used unit operation in water treatment and elsewhere in chemical industries. It has occasionally been used in hydro-metallurgy for treating plating, pickling, and rayon wastes Concerning ion exchange in extractive hydrometallurgy—for treating ore leach solutions— the literature prior to the Geneva Conference has given only hints."-" Yet most of the ore leach plants now being built or completed in the last three years use ion exchange for this purpose. Most of these plants are used for extracting uranium. The overall process for leaching low grade uranium ores and the history of its development have been given in the authors' previous papers.',' The object of this paper is to discuss certain engineering aspects of the new application of ion exchange to recover dissolved values from ore leach solutions. Necessarily the illustrations will be taken from the first application—to uranium metallurgy. Although ion exchange processes have been devised in which separation of spent residue from pregnant liquor is not required, as in the RIP process,"-'I only ion exchange operation, in which the resin is contacted with a clear solution, will be discussed in this paper. Uranium exists in acid leach liquors mainly as the cation UO," and can be adsorbed completely by cation exchange resins, but the adsorption is not selective as other cations such as Fe++, Fe+++, Al+++, Mg++, Mn", and Ca++ are also adsorbed. Uranium, however, forms complex anions with sulfate, phosphate," Carbonate"~"~ and even with chloride if the solution is strong enough.15 These anions can be adsorbed by anion exchange resins. The strong base anion exchangers have a very strong preference for these complexes and hence this adsorption is very selective. In this paper, the examples concern acid sulfate leach liquors from which uranium is adsorbed as UO,(SO,),-% and UO,(SO,),". Materials and Equipment Ion Exchange Material—Ion exchange materials include natural and synthetic; organic and inorganic; cationic and anionic; and weak, intermediate, and strong varieties. They consist of fragments or beads normally in the size range —16 to $50 mesh. The newer varieties have been developed to have greater stability, chemical strength, and/or capacity than earlier varieties. The resin used for uranium recovery is a strong base anion exchanger.* To make * Such as Rohm and Haas Amberlite IRA-400 series, British Permutit DeAcidite FF. Permutit lonac SE. and Dow Nalcite SAR. this resin, styrene plus a few percent divinyl benzene are polymerized into long chains with occasional cross links. This resin in bead form is then reacted to introduce quaternary amine groups onto most of the aromatic rings.' These resins are water-avid gels of specific gravity of about 1.1, which shrink and swell by osmosis when the ionic content of the surrounding solution is changed. The beads which are shown in Fig. 1 can be broken like an onion by rapidly replacing 15 pct H,SO, with water. This organic gel can also be broken by mechanical handling as by a centrifugal pump. Otherwise it is remarkably stable. It is unharmed by fairly strong acid or alkali, oxidizing or reducing agents, and heat up to 70°C. The strong base resin when completely in the chloride form (with a chloride anion on each quaternary amine group) holds over 107 g of C1- per dry kg. As all these chloride ions can be displaced by other anions, the resin has an exchange capacity of over 3 g equivalents per dry kg. However, the resin is sold and used by moist volume. The moist resin contains about 50 pct water, weighs about 43 lb per cu ft, has 40 pct voids, and an exchange capacity of over 1 g equivalent per liter of bed volume. Ion Exchange Equipment—Ion exchange equipment used for recovery of uranium from leach solutions is substantially identical to that developed for water treatment and other applications.'" The resin beds are held in closed tanks or columns which, in the uranium plants, have been standardized at 7 ft diam and 12 ft high. The resin bed

Jan 1, 1958

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

Discussion -of the paper of I. N. KNAPP, presented at the New York meeting, February, 1915, and printed in Bulletin No. 96, December, 1914, pp. 2783 to 2793. A. C. LANE, Tufts College, Mass.-Is there any noticeable effect in drilling against salt water? Mr. Knapp says that the mud settles very quickly when brine is added-. What is the effect when you strike a strong salt water ill boring? I. N. KNAPP.-You are supposed to have enough mud pressure in your well to keep the saltwater out. I have drilled against what I knew to be 80 ft. head of water, and hot water too at 99.5°; this water did not show until the well was bailed and the mud pressure reduced. HENRY Louis, Newcastle-upon-Tyne, England (communication to the Secretary*).-Mr. Knapp may be interested to learn that the use of mud in drilling through porous strata is much older than lie appears to be aware of. It has been used notably by Honigmann for boring shafts in Holland and in some of the adjoining portions of Germany. At the Oranien Nassau colliery, shafts about 12 ft. in diameter and 425 ft. deep were sunk in. this way-namely, by boring with a rotary borer, a thick mud puddle being pumped into the shaft, so as to maintain a pressure in the shaft greater than the hydrostatic pressure in the surrounding loose sands and thus keeping the sides of the shaft from collapsing. He will find references to this method in Das Abbohren von Schächten; Handbuch der Ingenieurwissenshaften, p. 134, also in the Transactions of the Institution of Mining Engineers, vol. xiii (1896-97), p. 155. The process appears to have been employed even before 1895, though I cannot give the exact date when it was first used.

Jan 5, 1915

By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By Arvid E. Anderson, Frank K. Cameron

The weathering of copper-bearing ores with the formation of a water soluble salt and the recovery of the metal by leaching and evaporation precipitation, are processes long known, which have at various times been utilized with more or less commercial success. It is commonly assumed that the technical principles involved are quite simple and their application to a particular case easy. If these assumptions were true, we should anticipate a long list of uniformly successful leaching operations, which is not the case, and one would be justified only in calling attention to either unique or peculiar features of any particular enterprise; whereas, in studying the problems of the recovery of copper from the old workings of the Ohio Copper Co. in the light of available descriptions of other leaching projects, we have not found the assistance hoped for to guide us to the best realization of our own opportunities. It appears desirable, therefore, to call attention to these guiding principles, together with a description of the facts of accomplishment. Justification lies in the fact that the leaching and precipitation of copper at the Ohio Copper Co. mine in Bingham Canyon, Utah, is successful. This success is measured by an average monthly production of 600,000 Ib. of copper at an average operating cost, to date, of 3.85 cents per pound at the company's workings, or 6.32 cents per pound after paying shipping and smelter charges on the finished copper. A total of 17,076,099 Ib. of copper had been shipped to the smelter from the beginning of operations, August, 1922, to April 1, 1925. Probably these results can be bettered with further study and realization of the factors involved and the devising of methods of meeting them. It is now an assured fact that the enterprise will have a relatively long and continuously profitable life and that its reserves will not, nor cannot, be suddenly and permanently depleted. It is particularly noteworthy that the financing of this enterprise has been entirely from its earnings. The few hundred dollars necessary for the first experiments and production were obtained by the sale of used, and no longer needed, equipment from a mill belonging to the company; and all funds since required throughout the growth and development of the enterprise, from a few troughs with a production of 2000

Jan 1, 1926

By Dwight L. Baker, Alexander Knoll

The work herein reported shows that galena in certain organic solutions of fatty acids becomes coated with lead soaps, and that this coating is not only highly water-repellent but is also repellent to certain organic liquids, particularly those of high surface tension; i.e., nitrobenzene, diphenylmethane. Wetting Properties of Galena in Nonaqueous Fatty Acid Solutions When a "captive bubble"I is withdrawn from a polished, plane galena surface under a nitrobenzene solution of stearic acid, the air bubble shows a decided tendency to "cling" to the mineral surface. The contact angle, therefore, was greater than zero, although it was not large enough to be measured quantitatively by the captive-bubble method." When pure nitrobenzene was substituted for the nitrobenzene-stearic acid solution, no clinging of the bubble was observed; viz., contact angle = zero. Although the contact angle developed in air-galena-nitrobenzene-fatty acid solution was small, the organic solvent repellency of the galena surface was great enough to enable good recovery in a laboratory flotation cell2 In Table I are given the results of flotation experiments using several different fatty acids dissolved in nitrobenzene.

Jan 1, 1943

By Alexander Knoll, Dwight L. Baker

The work herein reported shows that galena in certain organic solutions of fatty acids becomes coated with lead soaps, and that this coating is not only highly water-repellent but is also repellent to certain organic liquids, particularly those of high surface tension; i.e., nitrobenzene, diphenylmethane. Wetting Properties of Galena in Nonaqueous Fatty Acid Solutions When a "captive bubble"I is withdrawn from a polished, plane galena surface under a nitrobenzene solution of stearic acid, the air bubble shows a decided tendency to "cling" to the mineral surface. The contact angle, therefore, was greater than zero, although it was not large enough to be measured quantitatively by the captive-bubble method." When pure nitrobenzene was substituted for the nitrobenzene-stearic acid solution, no clinging of the bubble was observed; viz., contact angle = zero. Although the contact angle developed in air-galena-nitrobenzene-fatty acid solution was small, the organic solvent repellency of the galena surface was great enough to enable good recovery in a laboratory flotation cell2 In Table I are given the results of flotation experiments using several different fatty acids dissolved in nitrobenzene.

Jan 1, 1943

By Arthur Notman

DURING the past fifteen years there has been a great change in the methods of treating employ-ment and discharge throughout industry. Perhaps nowhere has this change come more abruptly than in the metal mining districts of the West. In 1909, when I went to work for the Phelps Dodge Corporation in Bisbee, their operations were roughly arranged accord-ing to shafts in seven divisions, each employing from 100 to 250 men underground, and the mechanical department employing some 250 men, mostly on the surface. The underground divisions were each in charge of a foreman who had under him a night foreman and from two to four shift bosses on' each of two shifts. These foremen reported to the underground superinten-dent and he in turn to the superintendent of the mine department. The mechanical department was in charge of the master mechanic who reported to the superintendent of the mine department. RUSTLING A JOB IN THE OLD DAYS It was customary for men seeking employment to "rustle" the division foreman at the shaft during the lunch hour or at the close of the day shift and the master mechanic at the shops. There was no real attempt at interviewing the applicants for underground work. They simply filed in and out of the foremen's office-50 to 150 strong-in ten or fifteen minutes. If the foreman needed men, and he generally did; to replace those that he and the shift bosses had removed during the morning, he picked out those he knew or strangers who took his' fancy. The former in many cases were chosen for negative reasons rather than positive. In selecting the latter, the foreman felt that if they failed to show ability promptly, he could replace them the next day, and often did so. Even if these foremen had been skilful and well trained in the art of selecting men, it would have been impossible under the pressure of other duties to exercise that skill and experience in so doing. The conditions in the mechani-cal department were little better. About all that can be said in favor of such a method was that with a sur-plus of labor it "got by." The labor shortage brought about by the war disclosed its fundamental weakness.

Jan 6, 1923

By Noel H. Stearn

To the successful functioning of the geomagnetic method of exploration in engineering and geological practice there are two prime prerequisites : the measurability and the interpretability of significant magnetic anomalies. A magnetic anomaly may be defined as a permanent distortion of the earth's magnetic field, in order to distinguish it frog the distortions, either cyclic or irregular, which vary with time. So far as known, time fluctations have no directly assignable geologic significance in terms of rock formations, while anomalies may be considered to be directly caused by the difference in the magnetic properties within and between the formations of the substances that make up the earth's outer shell. As is effectively pointed out by L. B. Slichter,1 the effects which these differences produce on the magnetic field may be extremely minute or extremely great, depending upon the magnetic properties of the formations. Thus the actual anomalies may range from the infinitesimal to a magnitude considerably greater than that of the earth's field. The geomagnetic method of exploration has shared in the deluge of experimental effort which has lately swept geophysical prospecting to its present important place in engineering and geologic practice. But to date more of this effort has been expended upon the measurability of anomalies than upon their interpretability. The tendency has been to strive for the development of instruments and especially field techniques capable of measuring minute anomalies with a precision far beyond that for which there can be any hope of adequate interpretation other than as interesting phenomena having numerous possible causes. Such efforts, of course, are highly commendable in the field of so-called pure science, which includes the accumulation of undigested detailed observations and admits of interpretation by multiple hypotheses, but in engineering practice the factor of economy must enter. Those instruments and techniques are most desirable which can most rapidly measure the interpretable range of anomalies with the precision necessary

Jan 1, 1932

Prof. H. S. Munroe, New York City : In his reference to cop per-dressing at Lake Superior, p. 325, Mr. Douglas says that " the .. concentration .. . has been carried out with greatest financial economy,... I do not say with the greatest economy of min eral." And again, on p. 344, referring to the same, " it would not pay to reduce the quantity treated, and increase hand-labor, in order to save a few hundredths of one per cent. of copper." Mr. Douglas probably has in mind the fact that the copper lost is all included copper, locked op in grains of sand. To save this, the rock must be crushed finer. If the mesh of the stamp-screens be reduced, the stamps will crush less; and thus we shall have to reduce the quantity treated in the mill per day, while the labor re mains the same per day, or is increased per ton, as he says. Submitting to the loss of copper, however, is not the only solution of the difficulty. A large quantity of rich sand is now collected by the jigs, and it would be easy to save so much of this material that the escaping sands would be quite poor. What is wanted at Lake Superior, and at many dressing-works in this country, is an efficient crushing-machine to treat the sands thus collected. Abroad, we have the Heberle machine and the Schranz mill for this purpose, the latter being the more successful. The Heberle grinder was tried at the Calumet and Hecla mill for crush ing these rich sands, with what success I do not know. I should like to ask Mr. Douglas if we have no American crushing-machine that will reduce jig-sands to a fine state of division

Jan 1, 1894

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil'chenko' found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli' bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil'chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.' The presence of silicon in iron is said to reduce the activation energy for diffusion,' so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen' made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By C. D. King

THE advances in basic open-hearth practice which have occurred during the past decade, have been principally in the direction of the physical development of larger units, decreased fuel consumption and increased length of furnace campaigns. However gratifying the economies which have resulted from these improvements are, it must be granted that like advances in chemical, physical-chemical and metallurgical knowledge pertaining to open-hearth practice would have added greatly to these already attained reductions in costs and it is the purpose of this paper to stimulate the discussion and study of these phases of cooperation and their relation to ingot yields. DEFINITION AND CALCULATION OF LOSSES In discussing basic open-hearth yields, the writer refers to the ingot yields obtained in the process of converting pig iron, scrap and ore to steel. In this conversion some scrap is produced. The difference between the total weight of ingots and scrap produced and the original metallic charge, constitutes the loss. Basic open-hearth yields vary considerably, and while some of the divergencies can be explained metal-lurgically because of differences in slag analysis, proportion of pig charges, and character of steel made, there often remain differences that apparently do not readily disclose themselves. In reconciling yields by the usual accepted methods of calculation, one is often forced to evaluate large losses as "unaccounted for." Such a system is prone to accept these large losses as inherent to the operation and not susceptible of appraisement and correction. It is obvious that if the ingot yield, plus the scrap recovered subtracted from 100 per cent. determines the loss, a drop in yield may increase the loss or the scrap, and both contribute to a monetary loss. To be sure, one can subdivide these unaccounted for losses into various components, such as metallics in slag, free Fe in slag, spillage, etc., and thereby reduce the amount of losses considered as "unaccounted for." If empirical methods could indicate with some degree of accuracy all losses, however slight, the undetermined losses become appreciably smaller and resultant calculations will check actual

Jan 1, 1929

By AIME AIME

TRAINED as a mining engineer and with no little experience in the field of mining, his interests and activities later transferred to the alloying, fabrication, and physical metallurgy of nonferrous metals, principally silver, Robert H. Leach represents in his professional life both of the major phases of the fraternity of mining and metallurgical engineers. In his personal characteristics, his wide circle of true friendships, his kindly, sympathetic interest in the problems of his fellow engineers, be they the junior men of the mineral industries or the mature and experienced men, he typifies the characteristics and attitude so desirable in the professional man.

Jan 1, 1939

By J. E. Warren

In their analysis of Eqs. 29 and 30, the authors correctly deduce the following behavior limits for the "differential capacitance model". 1. When the rate group a is sufficiently large, the model reduces to that implied by Eq. 1, i.e., the simple convection-diffusion model. 2. When the rate group a is sufficiently small, the model reduces to that implied by Eq. 1 with 1 replaced by 1, i.e., the simple convection-diffusion model with a total pore volume equal to that occupied by the mobile fluid in the original model. Unfortunately, the authors' solution, Eq. C-1, to the transformed versions of Eqs. 29 and 30 does not exhibit the same limiting behavior. For example, as a approaches zero, Eq. C-1 reduces to the solution to Eq. 1 or, equivalently, the solution to Eqs. 29 and 30 for sufficiently large values of a. Therefore, it can be concluded that Eq. C-1 is not a general solution to Eqs. 29 and 30; this conclusion can be easily verified by substitution. I suggest that the correct form of Eq. C-1 is the following: It is generally realized that accounting for dispersion effects is an extremely tricky business; therefore no one should criticize the pragmatic approach of Coats and Smith who proceeded by accessible theory, made use of some available phenomenology, and who then took the trouble to check the consequences, against their own carefully undertaken experimental results. Here I should like to defend three assertions: (1) Coats and Smith copy the error of previous authors in the formulation of the so-called simple diffusion model (which error is then retained in their differential capacitance model); (2) improving the fit between data and the predictions of an arbitrary model by increasing the number of parameters is a triviality unless the parameters are disposable by being independently determined; and (3) existing experimental procedures lack sufficient resolution to clarify some current theoretical uncertainties. Taking first the view that all theoretical approaches (whether constructed by statistical, finite difference, or continuum arguments) tend to reduce to the same model form as fixed by the number and nature of the disposable parameters, one notices that the "finite-stage" model of Deans1 is equivalent to the Coats and Smith so-called differential capacitance model for the pertinent case where a

Jan 1, 1965