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By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970

By Noel H. Stearn

When the Age of Machinery was suddenly thrust upon civilization about the beginning of the 19th century, an unprecedented demand for mineral resources sprang up. This demand brought about the rapid development of the known ore deposits and the discovery of such other deposits as could be encountered by energetic and canny prospectors. Thus in the countries now reasonably accessible nearly all orebodies have been located except those which are totally concealed even from the eyes and "senses " of experienced and expert prospectors. The high rate of exhaustion of known ore deposits and the necessity of looking farther and farther ahead for raw materials as a matter of insurance on the stupendous capital outlays involved in mining, development, and conversion operations, have resulted in exceptional activity in three different fields of effort. The first is purely geographic. Prospectors are now penetrating the few hitherto inaccessible regions in the hope of stumbling upon exposed ore deposits or locating visible indications of their presence. The second is chemical. Industrial chemists and metallurgists are seeking to facilitate the exploitation of lower grade ores or to find methods of recovering valuable metals from common substances. In the third field of effort lie the activities of the economic geologist and the mining engineer, who endeavor to locate concealed ore deposits which would remain hidden from the prospector no matter how expert or conscientious he might be. Obviously the task which such a man must face is both exacting and indefinite, and the tools which he has heretofore been permitted to bring to it are, for the most part, abstract—a knowledge of certain fundamental principles and processes involved in the origin, occurrence, structure, and distribution of deposits of natural resources and of the rocks which form the environments of those deposits; and a process of reasoning by analogy supplemented by the use of the diamond drill, or such artificial exposure as the test pit, trench, shaft, or tunnel.

Jan 1, 1929

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington' have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4' and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick's law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.' By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.' (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick's law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By J. F. Tavernelli, L. F. Coffin

The deformation and fracture characteristics of eight metals subjected to fully reversed cyclic strain ranging from 0.2 to 50 pct were investigated at room temperature. Strain-hardening characteristics unique to the interna1 structure of a particular metal were found. Complete removal of the strain-hardening effects resulting from prior deformation was brought about by subsequent cyclic strain. Further support for the validity of the inverse relationship between the plastic strain range and the square root of the number of cycles for failure is given. THE resistance of materials to cyclic plastic strain is of interest both from a fundamental and practical point of view. It is now a well-accepted fact that fatigue failure in metals is a consequence of the localized slip deformation which occurs within the individual crystals of metal.'-' Hence the failure process should be strongly dependent upon the magnitude of the gross cyclic plastic deformation of the metal under conditions where this is a measurable quantity. Therefore, an experimental investigation of metals in which the cyclic plastic strain is the independent variable should shed new light on some of the basic aspects of the problem. From the practical point of view, there are many uses for information relating to the cyclic strain resistance of metals. One is the case of thermal stress fatigue where fatigue failure can occur as a consequence of a com- paratively few cycles of thermally induced mechanical deformation. Another is the mechanical working of metals where large cyclic strains are employed. In recent years several publications have appeared relating to the cyclic-strain resistance of metals,8-11 dealing mostly with the fracture aspects where the temperature is cycled simultaneously with the mechanical strain. Some work has been reported on the cyclic-strain resistance of metals at constant temperature, again oriented more toward the fracture aspects of the problem than the deformation aspects. 12-16 The present research investigation was undertaken to obtain information regarding the deformation characteristics of several metals whose structure-property relationships were simple and straightforward under conditions of both cyclic and monotonic strain. It has been shown for example that under cyclic-strain conditions some materials will strain harden, while other materials, particularly cold-worked structures, strain soften and these effects required further clarification.8,17-19 It was also de-

Jan 1, 1960

P. E. McKinney,* Washington, D. C.-Observation made after examination of a number of defective gun forgings, together with a history of their manufacture, has strongly suggested that so-called "flakes" and woody or fibrous fractures are not necessarily analogous and are often caused by entirely different conditions. While some flaked bars may show fibrous areas in the fracture, it does not necessarily follow that the conditions causing these areas are the same as cause the fibrous, or so-called laminated, structures so commonly met in gun forgings subject to transverse tensile test; the fibrous structure formed in some flaky bars are merely incidental to the conditions causing the flakes. It is believed that the so-called flakes, or bright silvery spots, are mainly due to inherent physical defects in the steel, which existed at the very origin of the steel, rather than metallographic defects caused by subsequent irregularities in mechanical or thermal treatment. While great care in forging and treatment may, in a measure, tend to overcome the evil effect of the defects, with many heats of ingots, no such precautionary measures are needed to produce perfect forgings- and with such heats of steel it would be impossible, no matter how carelessly handled, to produce intentionally a forging containing the defects commonly known as flakes. It has been found possible, on several occasions, to actually predict flaky forgings from an inspection f the ingot after it had solidified, and in such cases no amount of careful forging or heat treatment would prevent the occurrence of such defects in the forging. The inspection of the physical condition of the ingot, and especially the character of the shrinkage on. the top of the ingot, has been given too little thought and study in this connection.

Jan 5, 1919

By A. W. Ruff

The seismic wave produced by an explosive is very important in blasting. A true understanding of the wave is only important when considering possible structural damage to buildings located near the blast, but it is also of primary importance when considering rock fragmentation. Because of the importance of the seismic wave to fragmentation, a finda-mental study of the seismic wave and its effect was made at the Cananea Consolidated Copper Co.'s mine at Cananea, Sonora, Mexico. Strain gages were used to measure the strain in the rock when nearby explosive charges were detonated. The variance in the circuit voltage caused by changes in the resistance of the strain gage was measured with an oscilloscope and recorded with a Polaroid camera. CONFINED DRILLHOLE CHARGES To record the seismic wave from a confined drillhole explosive charge, a gage was cemented to the bottom of a 4-in diam drillhole. The horizontal gage hole and nine horizontal charge holes were drilled perpendicular to the center line of the 2-39 drift and 4 ft above the floor. The gage hole was 29 in. deep, and the charge holes were drilled so that each bottomed 1 in. deeper than the gage hole. The gage was installed with its axis horizontal and parallel to the 2-39 drift. The charge holes had the following horizontal distances from the gage: hole 3, 3 ft; hole 4, 4 ft; hole 5, 5 ft; hole 9, 9 ft; hole 10, 10 ft; hole 14, 14 ft; and hole 15, 15 ft. Figs. 1 and 2 show the relationships of the gage and the charge holes. Charges of 80 pct special gelatin, which weighed 50, 100, and 150 g were exploded in the charge holes and the seismic waves were recorded. All charges were stemmed with 200 g of mud and detonated with an electric blasting cap. Fig. 3 shows the recorded seismic waves. The reflected components of the waves were too weak to be objectional on these records. Table I shows the data taken from the wave forms. The approximate average velocity of a wave with a 9-ft travel distance was 12,900 fps. Since different charge weights were used, it was necessary to scale the data. The scaled maximum compress ion-strain data and the scaled maximum tens ion-strain data are shown in Figs. 4 and 5, respectively. Figs. 6 and 7 show the strain-distance data from Figs. 4 and 5 converted to a 1-lb charge. The results showed that the wave consisted of an initial compression pulse followed by a tension pulse. The amplitude of the tension pulse approached the amplitude of the compression pulse as the distance between the gage and the shot increased. The decay rate of the seismic wave is very important in the evaluation of the blasting characteristics of a rock. When high-amplitude stresses are produced, as in rock fragmentation, the rate of decay is much more rapid than when small amplitude stresses are produced. In underground mine blasting, the burdens are usually not greater than 6 ft and the decay is very rapid. The rapid seismic-wave decay rate in the fragmentation range means that in practice, if the minimum weight of powder is used to break a specified burden, only a very

Jan 1, 1961

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By T. A. Richard

We rejoice that the world-war is ended. We are proud of the part played by the English-speaking peoples—all doing equal honor to the traditions they share in common. One of the compensations for the calamity of the past four years is the fact that the Briton and the American, striving together in the cause of human liberty, have learned to understand and to respect each other. The mother country entered the fight resolutely at the beginning, while yet unready to meet the carefully prepared onslaught of the enemy; then the sons from the overseas dominions rallied to the old battle-cry eagerly and effectively; and last, but not least, the stepsons came from across the Atlantic, speaking the same speech, playing the same game, and fighting in the same clean way. It was a great foregathering of those that use the language of Shakespeare and idealize the principles of liberty for which the friends and associates of Shakespeare stood sponsor three centuries ago.' At a time like this it is pleasant to dwell upon the fact that the liberal Englishmen who organized the Virginia company were the pioneers of self-government on the American continent. The Virginia Assembly, convoked in 1619, was the first example of a domestic parliament to regulate internal affairs on this side of the Atlantic.2 The Governor of Virginia, Sir Edwin Sandys, had been a pupil of Richard Hooker at Oxford and from that political teacher he and his friends had imbibed the idea of combining civil liberty with constitutional order. To this group of large-minded Englishmen, the American colonists owed their liberal charters and their successive triumphs over the royal prerogative. Let it be noted that the American colonists had to deal with James II and George 111, the two smallest minds in the list of British kings. Another historical note, more pleasant to record, is the connection between the two principal groups of American settlers. In 1608, when the Pilgrim fathers, William Brewster and John Robinson, led their Separatist congregation to Holland and there prepared the expedition to America, they were assisted by Sandys and the Virginia Council, who were willing to share their privileges with them. When the Pilgrims set sail in 1620 they had the promise, obtained by Sandys from King James, that they should have freedom of worship,

Jan 1, 1920

By J. E. Warren

The mathematical problem considered by the author1 can be given another physical interpretation which is of some practical significance. The alternative physical problem involves the approximate behavior of a single well which is producing at a constant rate through an axially symmetric, horizontal fracture of infinite flow capacity which is located at the center, top or bottom of a uniformly thick, horizontal, homogeneous, anisotropic reservoir of infinite lateral extent which contains a single, slightly compressible fluid. Using Coats' asymptotic results, the wellbore pressure in the fractured system is given by the following equation.

By W. D. Forgeng, P. F. Wieser

MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.

Jan 1, 1964

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. ROBERT W. HUNT CHICAGO, ILL. (Term expires February, 1907.) VICE-PRESIDENTS OF THE COUNCIL. WILLIAM P. BLAKE TUCSON, ARIZ. THOMAS F. COLE DULUTH, MINN. IRVING A. STEARNS WILKES-BARRE, PA. (Term expires February, 1907.) HENRY AL HOWE NEW YORK, N. Y. J. B. GRANT DENVER, COLO. JAMES D. HAGUE NEW YORK, N. Y. (Term expires February, 1909.)

Nov 1, 1906

By G. G. Gunther, C. L. Boeke

DISCUSSION I. M. Symonds, (Cia. Minera de Penoles, Monterrey, N. L., Mexico)—Messrs. Boeke and Gunther have written most interesting papers describing their zinc de-leading operations. Mr. Gunther was kind enough to show me his operation last fall. Aside from the excellent results, I was most impressed by the ease of control. I had expected a difficult operation requiring careful control and supervision, but found one requiring little attention. The only disappointing fact of the separation is the poor copper recovery in the concentrate of the delead-ing float. The final zinc concentrate still has about 3 pct chalcopyrite, assuming the copper is chalcopyrite, and adversely affects the zinc grade. If the copper mineral is free, the poor recovery is probably due to the high cyanide concentration. Fortunately, about 75 pct of the copper is recovered before the pulp goes to the zinc circuit. Mr. Gunther's remarks about proper cyanide to zinc sulphate ratios cannot be overemphasized. Although our experience has been confined mostly to the conventional lead-zinc separation, we have found these ratios most important, and more important in the mill than in the laboratory. The laboratory appears to give optimum results over a wider range of reagent control than the mill, especially in regard to the effect of cyanide. In handling relatively high grade ores in the mill we usually find that ratios of cyanide to zinc sulphate of 1 to 10 or 20 or higher work best. Where there is a substantial amount of chalcopyrite present it has been noted that cyanide in the range of 0.02 to 0.10 lb per ton of ore is often beneficial in zinc rejection and possibly in copper recovery in the lead concentrate, while larger amounts, say 0.20 to 0.25 lb per ton, will float more zinc and cause a serious rejection of chalcopyrite. On an ore with 15 to 20 pct zinc content we have had to use 0.8 to 1.2 pounds of zinc sulphate per ton of ore with the above cyanide to obtain optimum results. Some time ago we made a laboratory study following Parral and Santa Barbara practice on an ore which had never a very satisfactory rejection of zinc in the lead concentrate. The results were not encouraging and a mill test was not run. Since then the study has been reopened using in the laboratory fresh zinc concentrate from the mill instead of one made in the laboratory. A reasonably clean lead float from the zinc concentrate was obtained. It has been checked several times and each time the zinc concentrate made in the mill responds and the one made in the labora-

Jan 1, 1953

By G. G. Gunther, C. L. Boeke

DISCUSSION I. M. Symonds, (Cia. Minera de Penoles, Monterrey, N. L., Mexico)—Messrs. Boeke and Gunther have written most interesting papers describing their zinc de-leading operations. Mr. Gunther was kind enough to show me his operation last fall. Aside from the excellent results, I was most impressed by the ease of control. I had expected a difficult operation requiring careful control and supervision, but found one requiring little attention. The only disappointing fact of the separation is the poor copper recovery in the concentrate of the delead-ing float. The final zinc concentrate still has about 3 pct chalcopyrite, assuming the copper is chalcopyrite, and adversely affects the zinc grade. If the copper mineral is free, the poor recovery is probably due to the high cyanide concentration. Fortunately, about 75 pct of the copper is recovered before the pulp goes to the zinc circuit. Mr. Gunther's remarks about proper cyanide to zinc sulphate ratios cannot be overemphasized. Although our experience has been confined mostly to the conventional lead-zinc separation, we have found these ratios most important, and more important in the mill than in the laboratory. The laboratory appears to give optimum results over a wider range of reagent control than the mill, especially in regard to the effect of cyanide. In handling relatively high grade ores in the mill we usually find that ratios of cyanide to zinc sulphate of 1 to 10 or 20 or higher work best. Where there is a substantial amount of chalcopyrite present it has been noted that cyanide in the range of 0.02 to 0.10 lb per ton of ore is often beneficial in zinc rejection and possibly in copper recovery in the lead concentrate, while larger amounts, say 0.20 to 0.25 lb per ton, will float more zinc and cause a serious rejection of chalcopyrite. On an ore with 15 to 20 pct zinc content we have had to use 0.8 to 1.2 pounds of zinc sulphate per ton of ore with the above cyanide to obtain optimum results. Some time ago we made a laboratory study following Parral and Santa Barbara practice on an ore which had never a very satisfactory rejection of zinc in the lead concentrate. The results were not encouraging and a mill test was not run. Since then the study has been reopened using in the laboratory fresh zinc concentrate from the mill instead of one made in the laboratory. A reasonably clean lead float from the zinc concentrate was obtained. It has been checked several times and each time the zinc concentrate made in the mill responds and the one made in the labora-

Jan 1, 1953

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By Pierre R. Hines

The first progress in American ore dressing practice was made in the mills of the Mother Lode in Calif., the Comstock Lode in Nev., and Gilpin County in Colo., during the years 1861 to 1870, when the ancient wooden stamp battery, with square wooden stems, was converted into the 'California' stamp made of wrought and cast iron, with round stems which rotated. Eli Whitney Blake invented the jaw crusher in 1858 for stone crushing, and it was soon used for crushing ore. F. W. Gates' gyratory crusher followed twenty years later. S. R. Krom, Thomas A. Edison, and others improved the Cornish rolls by increasing their size and spring pressures; the Symons Brothers made horizontal and vertical disc crushers; W. Ball and E. T. Leavitt designed powerful steam stamps for Lake Superior native copper ores; and jigs were mechanized. William B. Frue, a mill superintendent in the Lake Superior copper district, invented the vanner in 1874. Arthur F. Wilfley built his riffled concentrating table in 1895, just after Dr. Robert H. Richards commenced his Ore Dressing. The Wilfley table so changed concentrator flow sheets that Dr. Richards was compelled to revise his text, and its publication was delayed until 1903. The value of sizing or classifying before concentration was recognized. Dr. Richards had persuaded the Anaconda Copper Mining Co. to install round tables with special surfaces to catch the 'extremely fine free mineral.'l Gravity concentration had achieved almost every refinement for recovering or separating minerals by the difference in their specific gravities. However, one serious problem remained unsolved, i.e., how to retrieve the enormous loss of the extremely fine mineral in the slime portion of the ore. Slime, then, as now, was not a precise term due to the variation in the mineral composition of the ores and the different requirements in crushing, grinding, sizing, and classifying. At that time, slime was considered to be fine sand and colloidal material passing 100 mesh.2 Most sulfide ore minerals are more friable than their associated gangue minerals, so that crushing and grinding increased the proportion of the extremely fine ore minerals in the slime. Sparkling specks of galena, chalcopyrite, argentite, or ruby silvers, according to the ore, floating away on the tailing stream from vanners and slime tables, were familiar sights in the old gravity concentrators. Gravity concentration practice was aimed at recovering the ore minerals at the coarsest possible size because the recovery was higher and unnecessary

Jan 1, 1962

By H. C. Fiedler

SILICON-IRON strip with a cube-on-edge secondary recrystallization texture is made commercially as thin as 10 mils. With inclusions present to inhibit normal grain growth, a few grains, and these have the (110)[001] orientation, grow very large at the expense of the matrix grains. In the absence of inclusions, only normal grain growth occurs and the texture is not as strong as when it is developed by secondary recrystallization.1 Strip for use at frequencies of 400 cps and higher is made in thicknesses of 1, 2, and 4 mils by a process developed by Littmann.2 Attempts to develop a strong texture in these thin gages by the same methods as were used for the 10 mil and thicker strip were unsuccessful,2 and Littmann's solution to this problem was to cold roll the grain

Jan 1, 1963

By W. J. Helfrich, R. A. Dodd

Binary aluminum solid-solution alloys containing various amounts of silver, magnesium, and zinc were prepared by careful directional solidification, and the hydrostatic and X-ray densities were compared. With the exception of the Al(Ag) alloys, the X-ray densities were consistently greater than the hydrostatic measurements, in agreement with earlier observations by Ellwood. In contrast to Ell-wood's interpretation in terms of vacant lattice sites associated with Brillouin zone effects, a tentative explanation based on the existence of solidification microshrinkage was favored. This hypothesis was confirmed by an examination of Al(Zn) alloys prepared by vapor diffusion of zinc into aluminum. The hydrostatic and X-ray densities were now in very close agreement, and it was concluded that the filling of Brillouin zones in aluminum solid-solution alloys does not necessarily result in the formation of defect structures containing an excess of vacant lattice sites. ThE existence of defect structures of the vacancy type in alloys in which the excess vacancies have an electronic rather than a thermal or mechanical, and so forth, origin is well recognized. Examples of incomplete lattices of this type are to be found in the Ni-Al,1-3 Fe-Ni-A1,4 c~-Ni-Al,5 Fe-Cu-Al,= and Co-A17 systems. These defect structures are of a special kind in that the intermediate phases possess an ordered atomic arrangement or superlattice, and in some instances the vacancy concentration may be unusually large, e.g., at 45.25 at. pet Ni in NiA1, approximately 8.8 pet of the lattice sites are unoccupied. Ellwood8-10 has reported similar defect structures in the aluminum solid solution alloys of the Al-Zn and A1-Mg systems and in alloys of the Au-Ni system." In Al(Zn) the (apparent) vacancy concentration rose, somewhat irregularly, to a maximum of about 2 pet vacant sites at 25 at. pet Zn, while in Al(Mg) the (apparent) vacancy concentration increased continuously to 1.7 pet at 15 at. pet Mg. An explanation in terms of Brillouin zone overlap was attempted, although Pearson12 has pointed out the difficulty of reconciling the observations with zone theory. However, the possibility of the effect being caused by the Fermi surface just touching a plane of energy discontinuity inside a prominent Brillouin zone has, in general, been accepted. In fact, Massal-ski13 has interpreted Ellwood's8 observations as confirmation of Leigh's14 theoretically predicted zone overlap occurring at approximately 2.67 electrons per atom. Unfortunately, Massalski was apparently unaware that Ellwood9 had revised his earlier results considerably, and the revised data did not confirm Leigh's analysis. Ellwood's clata were reexamined by the present authors who noted a possible correlation between the percentage defects as a function of alloy composition and the temperature interval of solidification measured from the respective equilibrium diagrams. This suggested an explanation in terms of shrinkage porosity rather than vacant lattice sites, and pointed to the desirability of reexamining appropriate alloy systems using: both Ellwood's method of specimen preparation (casting followed by wrought fabrication) and alternativ'e methods, i.e., diffusion, which might be expected to minimize, or even completely obviate, microporosity. ALLOY PREPARATION 1) Cast Allolys and Aluminum Single Crystals. Al(Ag), Al(Mg;l, and Al(Zn) alloys of various compositions up to 20 at. pet silver, 13.5 at. pet mg, and 30 at. pet Zn were prepared by melting under helium and casting into graphite molds. In the first two systems, the maximum alloying addition was quite close to the limit of solid solubility, but the possibility of transformation to a' during quenching somewhat restricted the suitable Al(Zn) composition range. The alloys were prepared from high-purity aluminum, a lot analysis showing 0.002 wt pet Cu, 0.002 wt pet Fe, and 99.996 wt pet A1 by difference. The silver, magnesium, and zinc were of 99.99+, 99.98+, and 99.998 wt pet respectively. Each composition was analyzed chemically. The as-cast ingots measured 7/16 in. diam and 5 in. length. One in. was removed from the top of the ingot, and the bottom 3 in. was machined to 0.275 in. diam; a point was also machined on the smaller diameter end. The remainder of the original ingot served as a top riser during subsequent remelting and controlled solidification. The machined ingots were now remelted using a Bridgman soft-mold technique to ensure directional solidification and, therefore, a minimum of micro-shrinkage. Alumina powder was used as mold material contained in an alundum thimble, and this crucible was placed in a helium-filled Vycor tube. The assembly was lowered through a suitable temperature gradient at approximately 0.5 in. min-l, and the risered portion of the casting was subsequently removed by sawing.

Jan 1, 1962

By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

The effect of such variables as feed size, particle shape, cleavage, and hardness on the relative proportion of impact, abrasion, and chipping events in a tumbling mill is demonstrated. The concept of an average event, which is a combination of the three comminution mechanisms, is introduced. It is postulated that the average event in a particular mill determines not only the size distribution but also the energy-size reduction relationship for the comminution process. Fragmentation of particles in tumbling mills appears to result from a combination of impact, abrasion, and chipping grinding.' The relative rates of size reduction attributable to any of the basic grinding mechanisms must depend upon a number of variables, such as feed size, particle shape, hardness, and the number and kind of particles in the mill. The purpose of this paper is to show experimentally how these variables in the properties of materials affect the size distributions obtained by grinding the material's in a laboratory tumbling mill. The resulting size distributions will be intetpreted in terms of a combination of three comminution mechanisms. METHODS AND MATERIALS In this study, minerals of widely differing properties were ground either separately or as mixtures in laboratory mills using rods or balls for grinding media. The materials used include quartz, Tuolomne, limestone (99.8% CaCO3), barite, corundum, galena, pyrite, glass beads, and crushed glass. The mill used was 8 in. in diam. and 9-1/4 in. long. For the ball milling tests, 17.6 kg of steel balls (36: 7/8 in. balls, 178: 1 in. balls, and 44: 1-1/8 to 1-1/4 in. balls) were used. For the rod milling experiments, 17.6 kg of steel rods 9-1/16 in. long (25: 5/8 in., 10: 3/4 in., and 5: 7/8 in. in diam.) were used. In each test, 1 kg of solids were ground wet at 60% solids at 77 rpm. In all cases except where otherwise specified, the feed to the mill was 4 x 8 mesh material. Size distributions of the ground products were determined by a wet-dry sieving procedure with Tyler series sieves. Size distributions of mixed products containing limestone were determined by dissolving the limestone with acid and sizing the residue. EXPERIMENTAL RESULTS AND DISCUSSION If the size distribution of the product from a tumbling mill depends upon the relative proportion of impact and attrition (abrasion and chipping) events, altering the grinding conditions may change these proportions and consequently alter the size distribution of the product. Data to illustrate this point can be taken from Gaudin's classic 1926 paper.2 In one series of experiments, Gaudin ground quartz of different initial sizes for four hours in a laboratory ball mill with 7/8-in. balls. In Fig. 1, his data are reproduced as the cumulative fraction finer than the stated size for the following initial feed sizes: 13.3 x 9.4 mm, 6.7 x 4.7 mm, 2.6 x 1.6 mm, and 0.83 x 0.59 mm. As the feed size was decreased, a dramatic change in the shape of the size distribution curves took place, even though the amount of minus 100-mesh

Jan 1, 1964