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By M. Kitada, U. Kawabe, F. Ishida, T. Doi

The relations between micros tructures and critical current density in transverse magnetic field were experimentally investigated due to each transformation of the 0 to 0' + P" phases at 700' C for superconductmainly examined using replication electron microscopy. The ß' or a precipitates were found to pin down magnetic flux lines in these alloys. The effects of precipitation upon the critical current density were discussed in relation with the size, spacing, and characler of these precipitates. HIGH magnetic field superconductors, such as Nb-Zr, Nb-Ti, and Nb-Zr-Ti alloys, have been recently put to extensive practical use as winding materials for superconducting magnets.13 The critical current density of these hard superconductors under an applied magnetic field is an important characteristic for magnet materials and is very sensitive to metallurgical structure. It is generally known that the critical current density is increased by introducing dislocations and precipitates into a superconductor; that is, dislocations and precipitates are presumed to be barriers that hinder quantized flux lines from moving.4'5 Theoretical6'7 and experimental analyses of the motion of flux lines and the interaction between flux lines and various defects have already been reported by many authors. Metallographic analysis of high magnetic field superconductors such as Nb-Zr and Nb-Ti is difficult, so that no quantitative relationship between microstruc-ture and critical current density has been established yet. In this paper, the effect of precipitation on the critical current density in magnetic field was investigated for two superconducting alloys, Nb-40Zr-10Ti and Nb-5Zr-60Ti. In these alloys the resistive critical field H, at 4.2oK was about 100 kG and the critical current density Jc at 80 kG was of the order of 104 amp per sq cm.13-l5 The superconducting properties were examined in relation to the microstructural changes due to transformation of i) the ß to ß' + ß" phases at 700°C for Nb-40Zr-10Ti alloy and ii) the ß to a + ß phases at 500°C for Nb-5Zr-6OTi alloy. The effect of size, spacing, and character of precipitates on flux line pinning was in particular examined. The microstructures were studied by means of residual resistivity, microhardness, and tensile strength measurements as well as by X-ray diffraction, optical, and replication electron microscopies. I) EXPERIMENTAL PROCEDURE Pure niobium, zirconium, and titanium, in the form of rods 0.8 cm in diam, served as raw materials. Results of chemical analyses of these rods are given in Table I. Ingots of the alloys, 0.4 cm in diam and 3 cm in length, were prepared by means of levitation melting, utilizing a copper mold in an argon-gas atmosphere. Samples from the ingot then were cold-worked by grooved mill to 0.2 cm in diam, heat-treated homogeneously (in the ß phase region) for 5 hr at 1100° in a vacuum of 1 x 106 Torr, and finally cold-drawn to 0.025 cm in diam. For heat treatments, samples were wrapped in niobium foil and sealed in an argon-gas atmosphere in fused quartz capsules. Water quenching was done after each heat treatment. Subsequently H-J, were performed at 4.2° by slowly transporting the current through the samples 4 cm long, under transverse magnetic field, until the least detectable resistive terminal voltage was observed. The resistive critical field H, was taken as the field at which 100 pv appeared at 4.2°K across a sample 3 cm in length, with a current of 5 ma. The critical temperature T, was measured by means of a conventional four-probe resistivity technique and taken as the temperature at which the sample resistance reached one-half of full restoration of the normal-state resistance with a current l ma flowing through a sample 2 cm in length. Precipitates were observed by means of optical microscopy and carbon replication electron microscopy. The etching solution consisted of 5 ml HF, 10 ml H2SO4 10 ml H2O2, and 50 ml H2O, and shadowed carbon replicas were examined in a itachi HU-11 electron microscope operated at 50 kv. X-ray diffraction photographs were taken by a 11.46-cm-diam Debye-Scher-rer camera using copper Ka radiation. The micro-hardness was measured under a load of 200 g using

Jan 1, 1969

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By M. G. Benz, J. F. Elliott

Otto Schaaber (Institut für Harterei-Technik, Bremen -Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By N. A. Gokcen, S. Fujishiro

The dissociation pressure of Cr3C2 has been measured in the range of 1908" to 2237°K by means of graphite Knudsen effusion cells. It has been found that Cr3C2 vaporizes according to the following reaction: 1/3 Cr3C2 (s or 1) = 2/3 C (graph.) + Cr (g). The equilibrizcm pressure, P, of Cr (g) is found to be log Ps=- - (21,194/T) + 6.525 over solid Cr3C2 and estimated as log P, = - (19,535/T) + 5.76 over liquid Cr3C2. CARBIDES of chromium are of great importance in alloy steels and cemented carbides. The published data on their therm odynamic properties at high temperatures, however, are meager. The heat capacity and change in entropy of Cr3C2 were determined calorimetrically by Kelley and Moore1 in the range of approximately 50" to 300°K, and by Oriani and Murphy2 from 297" to 1188°K. The standard entropy of Cr3C2at 298.15°K, obtained by Kelley.7 was later confirmed by DeSorbo.4 Equilibrium in the reaction was investigated by Boericke.5 A recent tabular summary

Jan 1, 1962

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period Mar. 10, 1917, to Apr. 10, 1917. George S. Blair, Pittsburgh, Pa. E. P. Mathewson, Toronto, Canada. H. M. Boylston, Cambridge, Mass. T. Poole Maynard, Atlanta, Ga. F. J. Brule, Toronto, Canada. . W. J. Mead, Madison, Wis. M. B. Cohen, Miami, Ariz.. D. G. Miller, Denver, Colo. W. M. Corse, Buffalo, N. Y. P. N. Moore, St. Louis, Mo. F. G. Cottrell, Washington, D. C. R. H. Morris, Ansted, W. Va. E. C. Cross, Cleveland, 0. W. J. Morrison, Toronto, Canada. Nelson Dickerman, San Francisco, Cal. M. F. Ortin, Petrograd, Russia. F. N. Flynn, Chuquicamata, Chile. G. W. Paymal, New York, N. Y. F. L. Garrison, Philadelphia, Pa. Edward H. Perry, Boston, Mass. J. S. Grasty, Charlottesville, Va. 0. G. Petersen, Somerset, Ky. H. D. Hibbard, Plainfield, N. J. H. C. Price, Bartlesville, Okla. H. L. Hollis, Chicago, 111. C. A. Richardson, Toronto, Canada. F. H. Jackson, Marysvale, Utah. Hallet R. Robbins, Vancouver, B. C., Can. W. Strickler Jones, Silver City, N. M. A. H. Rogers, Boston, Mass. E. B. Kirby, St. Louis, Mo. H. G. Smith, Princepulca, Nic. J. M. Lovejoy, Electra, Tex. Edwin G. Steele, Van Horn, Tex. A. F. Lucas, Washington, D. C. 'S. A. Taylor, Pittsburgh, Pa. Edwin Ludlow, Lansford, Pa. A. P. Thompson, Salt Lake City, Utah, E. Francis McCrossin, Birmingham, Ala. Milton A. Allen is now engaged in the New York office of Messrs. Arthur L. Pearse & Co. Percy E. Barbour, managing editor of the Engineering & Mining Journal, has been appointed, by Governor Whitman, Deputy Superintendent of Police of the State of New York.

Jan 6, 1917

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By Myron Rodgers

IN rock- or ore-crushing tests all data, in order to be valuable for study and comparison, should be obtained and tabulated under conditions as uniform as possible. The results of many such tests have no value for comparison, because of incomplete data and the lack of uniform conditions, screens and scale of sizing, etc. The purpose of this paper is to suggest a form of standard specifications which may be developed by the Milling Committee and approved by the A. I. M. E. for rock-crushing tests. It is not intended to discuss any theories of rock crushing. Reports of rock-crushing tests should include the following details: 1. Description of the machine employed (jaw or gyratory crushers, rolls, stamps, tube mills, Chilean mills, etc.). 2. Method and material (timber, concrete, etc.) of foundation. Much power is dissipated in the vibration of poor foundations. 3. Locality from which the rock or ore was obtained, and geological, mineralogical, and physical characters of the material. 4. The power consumption of the machine running with no load and with full load, the unit of power being 1 hp, per 24 hr. 5. The capacity of the machine in tons (of 2000 lb.) per 24 hr. 6. The duty in tons per horsepower-day. 7. The screen analysis of feed and product by the proposed A. I. M. E. standard screen scale. On the foregoing statement, the following remarks are offered.

Jan 9, 1915

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

Aalde, Kaare. ('40) Gen'I Del., Bisbee. Ariz. Aase, Glenn D., ('40) Univ. of North Dakota. Grand Forks. N. D. Abadesco, Enrique A., ('39) College of Engrg.. Univ. of the Philippines. Manila, P. I. Abbott. John L., ('40) Colorado School of Mines. Golden. Colo. Abdul-Ahad, A., ('39) Montana School of Mines. Residence Hall, Butte. Mont. Abreu, Ovidio M., ('38) Univ. of Nevada, Reno, Nev. Acomb, Allen. ('41) Louisiana State Univ., Box 1970, University. La. Acosta S., Gonzalo. ('40) Univ. of Texas, Univ. Sta., Box 1785. Austin, Tex. Adam, Howard W., ('41) Montana School of Mines. Butte, Mont. Adams, Albert, ('381 New Mexico School of Mines, Socorro. N. M. Adams. Charles W., ('39) Michigan College of Min. & Tech., Houghton, Mich. Adams. H. Travis, ('39) 316 South -5th St., Bur¬bank. Calif. Adams, Jack L., ('39) Univ. of Oklahoma, Nor¬man. Okla. Adams. John W., ('41) Colorado School of Mines, Golden. Colo. Adams. Lewis J.. ('39) 402 Del Mar Blvd., Corpus Christi, Tex. Adams, Rob L., ('40) Agricultural & Mech. Col¬ lege of Texas. Box 600, College Sta., Tex. Adamson. Charles R., ('41) Univ. of Utah, Salt Lake City. Utah.

Jan 1, 1941

By Richard M. Foose

MOST of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of roofing granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (Mining Technology, March 1944). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. MINING AND MILLING Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast southwest direction along the strike of the slate cleavage and are about 200 ft. wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, 1-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935 and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5º slope and in some of them there was stoping. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about 2-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus 2-in. product moves to a storage silo by bucket

Jan 1, 1945

By John Jermain Porter

(San Francisco Meeting, October, 1911.) THE value of any particular ore, coke, or limestone, for iron-making, depends upon its effect, first, upon the quality or value of the resultant product; and second, upon the cost of smelting. The factors under the first head are the percentages of phosphorus, manganese, and other elements, which remain in the pig-iron ; while those under the second head are the percentages of iron, carbon, or lime, the slag-forming constituents, which must be fluxed, and any other ingredients which give rise to variations in cost of fuel and flux. The first of these criteria of value is perhaps not capable of being reduced to a general formula embracing all cases, since it must vary to a great extent with market-fluctuations. For example, Bessemer pig is worth sometimes more and sometimes less than foundry-pig ; and the premium paid for high manganese varies within wide limits. The second, or smelting-value, however, can be expressed numerically with a fair degree of accuracy; and it is with this phase of valuation that the present paper is concerned. The utility of a means of comparing numerically the relative smelting-values of different ores, cokes, and limestones, is self-evident, although it may not have importance in Northern practice, where materials are largely standardized. On the other hand, there are, especially in the South, many furnace-managers who must use a great variety of materials of widely varying grade; and it is with special reference to this district, and in connection with the efficiency-methods which I have elsewhere proposed,1 that the methods herein described were devised.

Mar 1, 1912

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.' Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

By Alfred H. Brooks

The developments of the past five years have shown that Alaska, as a field for mining, stands in the first rank among the possessions of the United States. Its annual gold output is now about $8,000,000. It produces silver, copper and coal in commercial quantities and its recently discovered tin and petroleum promise to become important products. Concurrent with the gradual development of this wealth, the mining public has ceased to regard the territory simply as an arctic province where a few placer-miners struggle with adverse conditions to secure a grub-stake or a modest fortune. Of late years there has been a large influx of capital to investigate its mineral resources, but in its area of nearly 600,000 sq. miles there still remain large, unexploited and little-known fields. This work of investigation has been carried on under adverse conditions, and reflects credit on all who have shared in it, whether prospectors, mining engineers, or geologists. It is the purpose of this paper to outline briefly what has been, and is being, accomplished toward furthering the knowledge of Alaska's mineral wealth, and in this connection to present a brief history of the operations of the United States Geological Survey in the territory. A list of the publications of the Geological Survey, which pertain to Alaska, is presented as an appendix, in the hope that it may prove useful to those who are interested in the mining of this northern province. During the Russian occupation of Alaska, from 1783 to 1866, but little attempt was made to delineate its geographic features or to study its geology and mineral resources. The Russian-American Co., which long held control of the territory, was entirely absorbed in the exploitation of its fur trade,

Jan 1, 1905

By Richard A. Walker, John P. Hager

The thermodynamic properties of the Pb-Au system have been determined between 750" and 1075°C by means of the cell Mo, Pb(1) |(PbO-SiO2){l) , SiO2(s) |Pb-Au(1), Mo The activities of lead and gold exhibit negative deviations from ideal behavior; the values of ? pb and ? the raoultain activity coefficients at infinite dilution, being 0.24 and 0.25, respectively, at 1200°K. The liquidus curve for the gold-rich region of the Pb-Au phase diagram has been determined from measure-ments on seven alloy compositions in the two phase region (liquid + Au(s)). The standard free energies of formation of Au2O(l) and Ag2O (1) have been estimated from cell measurements obtained by replacing the alloy electrode with pure liquid gold and silver. A new integral molar heat of mixing curve for the liquid Pb-Au system is presented and the results of previous studies discussed. The contribution of HM to FE was found to be small relative to TSE. THE use of galvanic cells of the type A(l) |A+Za|A - B(l) [I] provides an accurate means for the thermodynamic study of liquid alloy systems. In Part 1&apos; it was shown that cells of type [I] may be extended to higher temperatures and to a wider range of alloy systems if the ion A+Za is incorporated in an appropriate molten oxide phase, rather than in the classical fused salt electrolyte. In the following investigation the experimental method is extended to an investigation of the thermo-dynamic properties of the Pb-Au system by use of the cell: Mo, Pb(l) | (PbO-SiO2)(l), SiO2(S) |Pb-Au(l), Mo [] Previous measurements on liquid Pb-Au alloys were obtained by Kleppa2 by electromotive force measurements on a galvanic cell involving a molten chloride electrolyte. These measurements were confined to temperatures less than 830°C and compositions with X Pb > 0.2 because of the instability of the cell at higher temperatures. Later measurements by Kleppa3 on the heats of formation in the composition range 0.67 < Xpb < 0.98 were not consistent with the results by electromotive force measurement. The purpose of the present study is to extend the temperature and composition range of the thermodynamic properties and to obtain an independent measure of the integral molar heat of mixing over the entire composition range.

Jan 1, 1970

By Eugene A. Stephenson

NUMBER of noteworthy events in the petroleum industry may be reported for 1941, of which the most spectacular was doubtless the rise in the daily rate of crude-oil production to a peak of approximately 4,300,000 barrels. This enormous daily rate did not ensue from the furor of flush pools but represented for the most part merely a slight additional daily delivery from many wells that had previously been operated on a more restricted basis, in line with good conservation practice and also from the adroit increase in the number of days per week by the Texas Railroad Commission. Another important fact was the increase in price throughout the Mid-Continent area from the static level of $1.02 for 36°, A.P.I., crude, to $1.17 per barrel. Efforts to elevate the price above this point have met with severe opposition from the O.P.A.. as has also a similar effort by the PennsyIvania Crude Oil Producers&apos; Association, but the vastly increased costs for materials and labor may shortly give the industry the enhanced price which it has long deserved.

Jan 1, 1942

By Hon. Tasker Oddie

DURING the closing days of the last Congress a resolution was passed, creating the Senate Com-mission of Gold and Silver Inquiry. The resolu-tion charges the Commission with the responsibility to investigate and report to the Congress on Jan. 1, 1924, upon the following subjects: 1. The causes of the continuing decrease in the production of gold and silver. 2. The causes of the depressed condition of the gold and silver industry in the United States. 3. The production, reduction, refining, transportation, mar-keting, sale, and uses of gold and silver in the United States and elsewhere. 4. The effect of the decreased production of gold and silver upon commerce, industry, exchange, and prices. The personnel of the Commission is as follows: Senators Pittman, Sterling, Goodling, Walsh and Oddie. At a meeting on May 8, H. N. Lawrie, a mining engi-neer and economist, was appointed as Assistant to the Commission. The present situation with respect to the gold and silver mining industries is well illustrated by the follow-ing data: The total world production of gold (in dollars) for 1915 was $468,724,918, and for 1921, $329,915,101; as shown by the reports of the U. S. Mint; and for the year 1922, $306,793,000, which is based oh a prelimi-nary estimate; this indicates a decrease of 34.5 per cent. between 1915 and 1922. The total world production of silver (in fine ounces) for 1915 was 178,850,000 oz.; for 1921, 175,268,234 oz., a decrease of 2 per cent.

Jan 6, 1923

ALABAMA. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Belle Ellen.-Hutcheson, W. C. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co Dobbs, G. G., Box 97. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., 1. & R. R. Co. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Brown-Marx Bldg. Coxe, E. H. Tenn. C., I. & R. R. Co. Crawford, C. G., Tenn. C., I. & R. R. Co. Crockard, F. H., Brown-Marx Bldg. Ellis, E. E.,1515 Brown-Marx Bldg. Fairbairn C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Geismer, H. S., Keiser-Geismer Engrg. Co.

Jan 1, 1917

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman&apos;s results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman&apos;s demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman&apos;s experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman&apos;s experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman&apos;s experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman&apos;s Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author&apos;s reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Walter Crooke

Regenerative hot-blast stoves are now in general use in all parts of the world, and are so well understood and appreciated, that I need not take up your time with an account of their history and introduction into the United States. My object in writing this paper is to give you a short description of a stove that is now being very favorably received and adopted here (see drawing). The stove was first introduced into this country in 1887 by M&apos;Clure & Shuler (now M&apos;Clure & Amsler), who have the management of the patent right in the United States. The English design had to be modified to suit the exigencies of American blast-furnace practice, which, in many respects, widely differs from our English experience. In the first place, the fire-bricks used in America expand to an extent unknown in England, and it became necessary to make special provision for this by increasing the number of cross-walls, and by leaving a space at the top of the stove through which the lining could expand. The expansion laterally was, however, more difficult to provide for, as the combustion-chamber in the center, being the hottest part of the stove, must necessarily expand more than the outer walls, and therefore tend to squeeze up the flue-openings. On first introducing these stoves to American ironmasters, a feel ing seemed to prevail that a " four-pass " stove did not utilize the whole of its surface. They also had an idea that the " two-pass " stove let the burning gas go before all the duty had been extracted from it; so that it was found neceseary to design a stove of a special character to suit their wishes. Hence the "three-pass" chimney top stove now before your notice, the advantage claimed for which is that each stove is independent, requiring no underground chimney flue or stack, and can be erected at a very light cost. The working of these stoves has proved to be very successful wherever they have been introduced.

Jan 1, 1891

THERE are three chief production zones of tungsten ore in China. In the Province of Kiangsi mines are located at Kanchow, East River, and West River. Their combined production is understood to amount to 300 to 350 tons of ore per month, and their original exportation is made through the port of Kiukiang, largely to Shanghai. The second zone is in Kwangtung Province, the mines there being at Tayulin. Produc-tion reaches about 200 tons per month and cargo is gen-erally exported through the port of Hong Kong. In the Province of Hunan approximately 25 tons of ore are produced monthly in the mines at Ton-on. Tungsten ore from Kiangsi and Kwangtung Prov-inces is generally about 70 per cent WO, (tungstic acid), while that from Hunan is of lower quality, run-ning about 65 per cent WO3. Kiangsi ore is received from the mines in 100-1b. and Hunan in 224-lb. gunny sacks. No repacking is done except as it is made neces-sary by the condition of the sacks. Kiangsi Province contains the Chinese districts pro-ducing the largest amount of salable wolframite or tungsten. Many districts west and south of Kiangsi have been found to have wolframite deposits.-Com-merce Reports.

Jan 1, 1928