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By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By Fred C. Bond

THEM is acute need for a method that will measure the size distribution of finely divided materials, particularly when the particle sizes are smaller than the openings of the finest screen cloth regularly available for testing. Several methods and types of apparatus are in common use, but none are entirely satisfactory for all purposes. The commonest methods are microscopic grain counts, elutriation by liquids or air, and sedimentation. Valuable results have been secured by air elutriating devices, typified by the Haultain Infra-Sizer and the Pearson Air Analyzer. These are especially useful in obtaining sized fractions that can be examined and analyzed separately. They are particularly advantageous because the sizes of the samples produced are adequate for a considerable amount of subsequent manipulation and testing. The sedimentation methods, such as the Wagner and Klein turbidimeters, and the sedimentation balance, do not deliver sized fractions, but they do provide a means for reasonably rapid comparative determinations of fineness and surface area, which are important in many industries. The sedimentation balance consists essentially of a balance pan suspended in a liquid that contains falling particles. These are weighed as they settle onto the pan, and the time rate of settling is determined. The size distribution is computed from the settling rate. The balance appears to be inherently more accurate than any of the other methods, and it has served a useful purpose in the study of numerous problems, but there have been limitations which have restricted its scope of application. Because of the essential simplicity of the method, it was felt that intensive investigation might lead to modifications that would make it a valuable tool for the operators in industries that require precise information regarding the results secured from grinding equipment. A large number of size-distribution determinations below 200 mesh were required in connection with a particular research problem in fine grinding. The sedimentation balance was used in this investigation, and a technique was gradually developed that ultimately gave good results. A serious difficulty appeared early in the work. It was discovered that less material always settled on the sedimentation pan and more on the bottom of the containing jar than could be accounted for by calculation, and also that the material that settled to the bottom of the jar outside the edges of the pan was considerably finer than that on the pan. This segregation was so great that the distribution obtained for the finer sizes was obviously very much in error; material ground to about the degree of comminution of cement might have only 60 per cent of the calculated weight actually settling on the pan, and the error increased with the fine-

Jan 1, 1939

By G. G. Sarkar

SHARPNESS of separation and washing efficiency are often confused. The sharpness index indicates the precision of a washing unit; the washing efficiency takes into account not only the unit's precision but also the washability characteristics of raw coal and the near-gravity materials at the effective density of cut. A sound basis for evaluating the sharpness index is essential in comparing the sharpness of separation attained by different cleaning units. Sharpness Index and Related Criteria: Washing plant sharpness of separation has been well represented by Hancock's efficiency chart and Tromp's curve of migrated materials. Some useful coefficients derived from Tromp's curve—the error area, probable error, and imperfection value—have been widely used to measure sharpness of separation. These are defined in a number of papers presented at the first and second International Coal Preparation Colsference held in Paris (1950) and Essen (1954).1-5 In evaluating the performance of a dense medium separator at four different gravities, Yan-cey and Greer6 bserved that even with similar operating conditions and the same size grading of feed, the imperfection value of a washing plant varies through a greater range than the probable error. The present writer also observed the same type of anomalies in comparing the imperfection values of one plant which were determined under almost identical conditions. He therefore devised a graphical method to evaluate a washing unit's sharpness of separation and define it by a single coefficient, which is substantially independent of coal characteristics under normal operation of the unit. Unlike imperfection value, the new coefficient can be expressed on a percentage basis. Coal preparation engineers generally agree that the amount of misplaced material resulting from any separation in a washing plant is almost directly related to the amount of +0.10 sp gr (near-gravity) materials. In actual practice, however, misplacement is not restricted to the 20.10 sp gr range. It will be evident from a study of Tromp curves that this misplacement often extends over unequal specific gravity ranges on the two sides of the actual density of separation. The same condition exists for near-gravity ash distribution and the resultant misplacement of ash units during any separation. But so far as the same unit is concerned, the total misplacements bear a definite ratio to the amount of near-gravity zone materials that is affected by misplacements. This ratio should be constant not only for various densities of separation but also for different qualities of feed coal treated in the same plant. This ratio, multiplied by 100, directly represents the inefficiency of the plant. When the plant inefficiency value is subtracted from 100, the re- ' sult is designated as sharpness index. Evaluating the Sharpness Index: The method of evaluating the sharpness index is explained here with reference to Fig. 1. Fig. 1 is a reproduction of the familiar diagram used by Cerchar of France to represent the inefficiency of a separation in terms of "triangle of errors," which is a measure of organic loss. It will be observed that the characteristic (yield/fractional ash) curve of the raw coal represented by GHAPR

Jan 1, 1958

By AIME AIME

ON Sept. 24, 1875, a remarkable deposit of silver ore was discovered by James Ryan and Samuel Hawkes at the east base of Grampian Hill in central Beaver County, Utah.. A shaft was begun and had been sunk about 30 ft. in ore when the claim was sold on Feb. 17, 1876, to A. G. Campbell, Matthew Cullen, Dennis Ryan, and A. Byram for $25,000. To them is due the credit of having developed the mine and started the district on the road to its present state of prosperity. Their development resulted in proving the vein to a depth of over 280 ft. and about 2500 tons of ore was extracted and turned into bullion. In February, 1879, the mine came into the possession of the Horn Silver Mining Co., and since then over $65,000,000 worth of ore has been taken from the mine. Two smelters were built in 1878, near the mine; 400 men were employed underground, and 1000 on the surface, burning charcoal, hauling wood from the surrounding hills, and freighting and hauling hay for the hundreds of horses used in the work. Ore was hauled thirty miles to the

Jan 1, 1936

Jan 1, 1955

Jan 1, 1888

New Products Equipment

Jan 6, 1953

By C. Hanford Henderson

The belt of copper-bearing rocks of the South Mountain has attracted Attention principally iii the townships of Hamilton Ban and Liberty in Adams County, Pennsylvania, and in the southeastern portion of Franklin County. As the developments, thus far, have been almost exclusively limited to that area, the examination here described extended only within those boundaries. The region, being one of considerable interest geologically, has been the subject of careful study and description, both on the part

Jan 1, 1884

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.'

Jan 1, 1970

Jan 1, 1947

By Lewis T. Wright

(Pittsburg Meeting, March, 1910.) I HAVE long been aware that ferruginous copper furnace slags if fused in the electric arc will yield metallic iron containing copper, and in order to confirm this knowledge, and to obtain further information of the behavior of such slags in the high temperature and reducing conditions of the electric furnace, a number of samples of slag were fused in an experimental electric furnace. The results obtained, given in Table I., show that a very large amount of metallic iron was produced, and that this iron carried with it practically all the copper, gold, and silver, and more than 50 per cent. of the sulphur, of the original slag. The metallic buttons formed in the electric furnace were clean, hard, but not brittle.

Mar 1, 1910

By A. S. Malicsi, I. Iwasaki

Differential flotation of bulk sulfide concentrates from Duluth gabbro into copper and nickel concentrates could be implemented by first destroying the hydrophobic coating with ozone and then by recovering the copper concentrate with a copper-selective collector. A number of parameters involved in the use of ozone, such as the sequence and the conditioning time of ozone treatment, the pulp pH, and the level of xanthate addition, were investigated.

Jan 1, 1986

By Carl Henrich

I have read with particular interest that portion of the discussion by Anton Eilers referring to the high-lime (and also high-alumina) slags made by August Raht in 1881, while smelting the Horn Silver ores at Franklin, Utah. The two analyses of such slags, furnished by Mr. Raht to Mr. Eilers are: (a) Not determined in this analysis. (b) Not given in Mr. Eilers' paper. Oxygen ratio, A1 as base. I. 0 in acid: O in base:: 18.1:18.9:: 0.96:1 11. 0 in acid :O in base:: 18.7:17.5::1.06:1 Average: 18.4:18.15=1.01:l Oxygen ratio, AI as acid. I. O in acid: O in base: :23.2:13.8:: 1.68:1 11. O in acid: O in base::23.1:13.5:: 1.76:1 Average: 23.15:13.4 = 1.73:l By assigning to alumina the the of a base, Mr. Eilers deduces the formula 3Feo.-2SiOa + 4Cao.2SiO². The nearest approach to a simple formula expressing the average composition of these slags, which I can figure, is 9RO.Al2O3.6SiO2. Allowing a ratio of 4Feo : 5Cao, we have for this formula:

Jan 1, 1917

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre- Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining counties cover most of the highly mineralized section of the Front Range which extends from James- town to Breckenridge. As far as the writer is aware, uranium has been found only in the portion north-east of Lawson.

Jan 1, 1950

By B. Amero, W. Petruk, D. R. Owens, D. R. Morris

Samples taken at different heights in the lead blast furnace of Brunswick Mining and Smelting corporation were studied to determine the phases present in order to interpret the reactions In the furnace. The main phases in the blast furnace feed are Pb3Ca2S13011, Zn ferrite (ZnFe204), and hardystonite (Ca2ZnSi207); rninor ones include lead and a Pb silicate. The temperature in the furnace varies from about 300°C at 4.2 m above the tuyeres to 1150°C at 1.1 m. There is no evidence of reactions in samples from points cooler than 800°C. Some reaction occurs between 950° and llOO°C and the lead sinter is nearly decomposed at about 1150°C. The first evidence of reaction was the decomposition of Pb silicate to lead and S102. At higher temperatures the Pb Ca2Si3011 decomposed to form lead and hardystonite (Ca2ZnS120rf. The Zn required for hardystonite was derived from the Zn ferrite which apparently re-equilibrated to a new Zn ferrite with less Zn. The decomposed sinter consists essentially of lead, hardystonite, wustite and a Zn ferrite with a low Zn content.

Jan 1, 1984

Jan 1, 1890

By P. H. Dudley

A quarter of a century of service of steel rails on our oldest railroads, many of which have changed their standard sections three or four times, has furnished, and is furnishing, excellent opportunities to study their wear and behavior in the track. Such experience is valuable for the design of new sections, now required to meet the constantly increasing severity of railroad service. Before presenting the new sections for consideration, I will briefly call attention to some features of past experience. For convenience of study, rails may be separated according to their weight and height into four groups, viz.: 1. Hails weighing per yard from 52 to 60 pounds, and 34 to 4 inches high. 2. " " " " " 60 " 72 " " 46 to 44 " " 3. " " " " " 72 " 90 ' 41/8 to 5 4. " " " " " 85 or more " " over 5 " I Experience in this country is confined mainly to sections in groups Nos. 1, 2 and 3. • During the past few years I have had the opportunity to run my car over many thousands of miles of railway laid with the principal sections in use, and to obtain diagrams showing their deflections, permanent set, and, in a great measure, their manner of wear. The First Group.—The first steel rails imported, and those manufactured here, were light sections—included in the first group—and many of them, being rolled in rolls used for rolling iron sections, have pear-shaped heads, 2 3/8 to 2 1/2 inches wide, the base being heavy and from 1/4 to 1/2 inch narrower than the height. These rails were laid upon ties of solid timber, at least 8 inches face, spaced 2 feet from center to center. The moments of inertia of these rails were low, only ranging from 8 for the lightest sections to 12 for the heaviest. The deflections were, of course, great; but the quality of the metal was excellent. It was physically hard and

Jan 1, 1890

By F. M. Doyle-Garner, A. J. Monhemius

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are hydrolyzed by water, typically at 130°C to 200°C (265°F to 392°F). Equilibrium hydrolytic stripping tests were done on Versatic 10 solutions containing various metals, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated [a]Fe2O3 Ni(OH)2 Cu2O + CuO, Mg(OH)2 and [?]Mn203 respectively, during hydrolytic stripping. Several mixtures containing iron precipitated magnetic spinel ferrites, MFe204. No other combinations formed mixed oxides. It is proposed that the mechanisms for hydrolysis and precipitation of iron in loaded Versatic solutions are similar to those for iron hydrolysis in aqueous solutions. Magnetic interactions between mixed carboxylate complexes are thought to be responsible for the homogenous nucleation of magnetic mixed oxides in preference to single oxides.

Jan 1, 1986

By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,' Konobejewsky,' Fujiwara," Goss,' and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By M. M. Singh

Coal mine operators are obligated to mitigate or plan for subsidence under the new regulations. This paper presents the types of subsidence control measures that may be employed to meet these requirements, which include: changes in mining methods, strata stabilization after coal extraction, construction of specially designed surface structures and foundations to accommodate ground movements, and comprehensive planning and coordination of surface land use with underground mining. The basic principles of these techniques, along with specific procedures that may be followed to implement them, are briefly discussed. Subsidence control methods that are currently being investigated are mentioned.

Jan 1, 1985