Search Documents

By Harry G. Dosh

Sillimanite, kyanite, and andalusite are aluminum silicates having the same chemical composition (Al2SiO5) and are used in the ceramics industry for the manufacture of high-grade refractories. Natural sillimanite with added corundum or other alumina to just short of mullite (3Al2O3 -2SiO2) proportions is unequalled for jobs wherein strength at high temperatures, resistance to spalling, and resistance to slagging by acid slags are desired. High-grade porcelain ware also requires these minerals. At the same cost, sillimanite would be preferred for most uses, but the lack of any large source of sillimanite bas given economic preference to kyanite or andalusite for special refractories and high-grade porcelain wares. Sillimanite-bearing schists were observed in Spartanburg County, S. C.; as early as 1937 by D. Hoye Eargle, geologist with the U. S. Soil Conservation Service. The mineral was not identified until 1942, when Miss Jewell Glass, of the U. S. Geological Survey, examined several of the deposits. This identification was confirmed in 1943 by Dr. Laurence L. Smith, of the University of South Carolina, when he examined the Spartanburg County deposits and found numerous additional occurrences of sillimanite schist in Greenville County. Subsequent work by the Bureau of Mines and the South Carolina Geological Survey has been responsible for the location of additional sillimanite-rich schist deposits in Spartanburg County. Between October 1, 1948, and November 21, 1948, the Bureau of Mines conducted an exploratory diamond-drilling project on the John Gideon property in the southeastern section of Spartanburg County (fig. 1) and drilled a total of 681.7 feet in six holes. Drilling indicated that the deposit is relatively shallow, as no ore was cut below the zone of weathering.

Jan 1, 1950

By Sedef Pinar Basag, Onuralp Yucel, Ahmet Turan

Niederschlag process is commonly used to produce metallic antimony. The process is a metallothermic process which is conducted in one step for metallic antimony production. Using this method Sb2S3 is mixed with coal and metallic iron and subjected to reduction. During heating, antimony sulfide is decomposed and sulphur combines with iron to form the matte phase. Metallic antimony is collected at the bottom of the crucible. In this study, evaluation of Sb2S3 concentrate, extracted and obtained from West Anatolian Region of Turkey was investigated by using Niederschlag process. The reductant stoichiometry, reduction temperature and duration were carried out in the experiments. Chemical analysis methods by using atomic absorption spectrometry (AAS) and X-ray diffraction spectrometry (XRD) techniques were used for the characterization of the concentrate, metallic nuggets and matte phases.

Jan 1, 2016

By MAX VOS

Lithium is the lightest and electrochemically most reactive of all metals. Renewed interest in lithium coincides with research in lithium batteries and power generation by atomic fusion. Ontario lithium resources are contained in spodumene pegmatites that can form where medium- to high-grade metamorphic volcanic-sedimentary formations are intruded by pegmatite and porphyritic granitic rocks. Spodumene pegmatites occur in at least twelve locales throughout northern Ontario, all of which are in the Superior Province of the Precambrian Shield. Tantalum, cesium, rubidium, beryllium, niobium and tin also were noted with lithium in spodumene pegmatites. Considerable potential remains for discovery of additional lithium and rare-element pegmatites in northern Ontario.

Jan 1, 1984

By T. Harrison

Surface coal mines in West Virginia are receiving stringent NPDES discharge limits for total recoverable selenium. With limits in the low parts-per-billion range, selection and implementation of proper sample collection and analytical methods are imperative for quality assurance and control and for consistency in results. Given the typical oxidized form of selenium in the water, the low limits and the large and variable flow rates from the watersheds, end-of-pipe treatment is difficult and cost-prohibitive to implement. Discharge locations in the remote and steep terrain exacerbate the problem. To evaluate options for end-of-pipe treatment at a Patriot Coal Corporation surface mining operation in West Virginia, CH2M HILL performed wastewater characterization for a range of key constituents and selenium species at three outfalls for selection and preliminary sizing of appropriate treatment processes. A preliminary evaluation of base and wet-weather flows was done to understand flow variability considerations for discharges. A conceptual evaluation of technologies to treat selenium to permitted levels was conducted in con-junction with order-of-magnitude life-cycle cost estimates.

Jan 1, 2010

By R. D. Doepker

The dissolution of metals from various metal-mine tailings has been studied through a series of submerged tailings batch tests at U.S. Bureau of Mines laboratories. Tailings selected for this study included both reactive (as determined by column leaching studies) and benign tailings. Metal mobilization in aerated (97 pct saturated with oxygen) samples appeared to be consistently greater than metal dissolution from stagnant (79 pct or 70 pct saturated with oxygen) waters. In the early weeks of the study, sulfate concentrations increased with solid-liquid contact time, while calcium dissolution remained nearly constant. Metal concentrations varied in relation to solid-liquid contact time and aeration. Leachate pH appeared to be nearly independent of solid-liquid contact time for basic tailings. Reactive tailings having both a submerged and a surface component demonstrated increased metal mobility.

Jan 1, 1990

By H. Arima, Y. Kudo

In general, the iron content of zinc leach residue produced by sulphuric acid leaching from calcine is disposed as jarosite or goethite into a tailing dam. More recently, these iron residues have been treated pyrometallurgically to avoid waste disposal. The Iijima refinery selected a different zinc leach residue treatment process for iron control when it was established in 1971. The Iijima refinery is the only plant in the world that has processed a zinc leach residue by the combination of SO2 pressure leaching and O2 pressure hematite precipitation. The process enhances zinc recovery and recovers gold, silver, copper, lead and rare metals in saleable by-products. This paper focuses on the two stages of autoclave application in the zinc leach residue treatment process. The detailed flowsheet and recent advancements to improve the quality of by-products are discussed.

Jan 1, 2004

By D. P. Roberts

This investigation aimed to simulate the experiments performed by Nic Gay (Gay, N.C.1976. Fracture growth around openings in large blocks of rock subjected to uniaxial and biaxial compression. International journal of Rock Mechanics and Minining Sciences and Geomechical Abstracts, vol. 13. pp. 231-243) on fracture growth around openings in blocks of rock subjected to uniaxial and biaxial compression, using the Elfen discrete element code. The results of the physical experiments indicated a number of trends that were successfully replicated in the numerical simulations, including crushing ahead of the face, the formation of a sub-vertical tensile fracture at centre-span, the formation of groups of fractures originating from the crushed face zone, the formation of large corner-to-corner fractures which precede sample failure, and linking of slot corner and sample corner fractures leading to sample failure. In addition, other features were apparent that were not reported by Gay. It is believed that these took the form of conjugate shear fractures (as reported by Gay in a previous paper) and other features that may have been altered or inhibited by the presence of pre-existing structure in the physical samples. It was found that the samples, though nominally made up of the same rock type, must have had significantly differing properties. The presence of pre-existing structures may have contributed to this discrepancy. Strain measurements from the physical experiments were reasonably well matched, except where the gauge lay directly in the path of advancing fractures.

Jan 1, 2012

By Anthony R. Przybylek, John M. Visnesky

INTRODUCTION Thermal dryers have been utilized for reducing moisture of bituminous coal since the late 1930's. Since that time, numerous changes in the coal industry have motivated advances in thermal drying technology. The purpose of this paper is to discuss the changes that occurred to dryer design and focus on current practices of fine coal drying. The major topics discussed in this paper are: - Early Thermal Dryer Design and Evolution - Current Drying System Design and Associated Components - Current Economics of Fine Coal Thermal Drying - Future Markets and Design Considerations EARLY THERMAL DRYER DESIGN AND EVOLUTION Background The practice of drying fine coal with heated air has been performed for more than one half century. Throughout that period, both Metallurgical and Steam coal producers have used this method for reducing the surf ace moisture content of their fine plant products. During the late 1930's and early 19401s, vibrating bed and flash dryers were used to per- form the drying duties. Closed water circuits and vacuum filtration had not yet been integrated into process circuitry and centrifugal dryers were in their early stages of development. During that same period, changes in mining practices were reshaping the distribution of coal to our processing facilities. Plants originally designed for the purpose of processing coarser fractions of coal were being burdened with additional quantities of fine coal. Those plants, unable to recover fine coal, would reject these solids to plant bleed. The higher incidences of stream pollution that resulted from these events prompted clean stream legislation and the need for new, more efficient fine coal recovery circuits. The coal processing industry responded to these needs by integrating closed water circuits and filtration into circuits. The fine coal filter cakes recovered exhibited poor handling characteristics by themselves and often required further dewatering to improve their characteristics. Flash dryers at that time were being used to dry the coarser products. For those facilities operating flash dryers, the solution to this new problem appeared to be simple. The filter cake was combined with the coarser (-1/4") coal and then introduced to the flash drying column for drying. The filter cakes, however, presented significant problems for the flash drying systems. Heavy lumps of filter cake could not be dispersed and conveyed by the rising hot air and as a result would settle out in the bottom of the column. This material, known as "drop-out", would then accumulate and require further handling. The solution to this problem was not an easy one. Sophisticated mixing equipment was employed to condition the feed to the dryers. As attempts to minimize drop-out with this approach failed, the only recourse was to collect the material with conveying systems and recycle it back to the plant or dispose of it. The additional costs of handling this material reduced the attractiveness of the flash systems and opened the door for the development of a new, more cost effective coal drying system. Due to the nature of the problems experienced by the flash systems, fluid bed systems were considered. Fluid bed dryers were being used in other industries at that time but had no operating history in the coal industry. Dorr-Oliver transferred technology from other industries and built the first fluid bed drying system for fine coal.

Jan 1, 1988

By T. Sekimoto, T. Kokubo, M. Yamamoto, K. Masuda, T. Moro, H. Sakamoto

The choking-free cyclone was developed primarily to remove solid particles suspended in a slurry containing fibrous materials, such as municipal solid waste. This cyclone is characterized by a screw conveyor at the underflow side of the cyclone. The screw conveyor has a hollow rotational shaft for air supply and is driven by a variable speed motor for discharge control. Even if the underflow discharge is highly concentrated, this type of cyclone can be stably operated without nozzle choking. High classification efficiency similar to that of a conventional cyclone can be obtained as a result of air introduction through the hollow rotational shaft. The recovery of organic matter and the removal efficiency of inorganic matter were actually improved by the application of this cyclone to municipal solid waste. After applying this cyclone to the desliming of fine sand, sand product of low water content was recovered.

Jan 1, 1980

1. Scope of project In South Australia, the Western Mining Corporation operates the underground copper and uranium mine Olympic Dam. The deposits concerned are enormous (approx. 570 million tons) and have been mined since 1988. At the end of 1996, Western Mining decided to increase the capacity of Olympic Dam from 85,000 t.p.a. to 200,000 t.p.a. Planning At this point, SIEMAG-GHH Mining Division was asked to carry out a study including the planning of the entire shaft hoisting operations and calculation of the investment and operating costs involved. With the assistance of Australian partners, the study was completed within a single month. The principal points of the study were as follows: ? Planning of the hoisting machinery for 1,375 tons per hour from the surge bin below ground to the discharge bunker above ground. ? Optimisation of the hoisting operation with regard to maximum availability and safety. ? Optimisation of the time schedule to minimise the financing costs of the investment. ? Statement of the investment and operating costs. ? Comparison of the technical data, design and availability of the planned machinery with reference plants. Construction of the plant Following acceptance of the study, the decision was taken within a few weeks to implement it. SIEMAG Transplan GmbH received the order to execute the entire shaft hoisting machinery on the basis of the study submitted. The decisive factors in placing the order were: ? Convincing study, adherence to schedule ? Reference to comparable plants elsewhere ? Reference with regard to availability.

May 1, 2003

The problems associated with achieving adequate accuracy for on-site axial flow fan performance measurements are discussed. The ability to test accurately rests heavily on equipment and installation design detail.Aerodynamic performance trials frequently cannot be carried out due mainly to the poor standard of installation design. In a majority of cases this results in unsteady, non-uniform inlet flow conditions to the fan. Details of installation design features and instrumentation, necessary for successful testing, are given for different types of installations and methods of testing. These cover both conventional practice, and new innovations which can provide solutions to difficult problems. Quantitative aspects of flow measurement are considered for various fan and duct configurations.Although the main emphasis is on large primary mine ventilation units which require on-site testing, the principles outlined have wide application to many other types of fan installation.

Jan 1, 1973

By Kermit Allen

Storing natural gas in solution mined salt cavities appears to be one of the more promising methods being considered by some major gas transmission companies for meeting peak demands. Historically, these companies have been faced with the problem of meeting peak demands when the source of natural gas is located hundreds of miles from the marketing area. Transcontinental Gas Pipe Line Corporation's position was further complicated because some of its offshore Gulf Coast gas supply wells may have to be shut in during hurricane alerts. Transco's solution was to construct. solution mined salt storage caverns adjacent to its pipeline near Eminence, Mississippi. (See Figure 1.) In 1965, Fenix & Scisson, Inc., was engaged by Transco to evaluate the feasibility of storing natural gas in caverns dissolved from salt at selected locations along Transco's pipeline to the East Coast. In June of that year a report was submitted to Transco concluding that this proposal was feasible and recommending several potential sites for storage development. Additional engineering and geological studies followed and in March 1968 the Eminence Salt Dome site was selected and storage construction began that year.

Jan 1, 1971

By W. R. Hamilton

THE knowledge of the existence of petroleum in Southern California dates back to the days of the missions. The presence of asphaltum and semisolid bitumen was reported at Santa Barbara in 1792, but no serious attempt was made to develop oil until Professor Silliman's optimistic report in 1865 started California's first oil boom. Wells were drilled in many counties of the State, but the equipment was unsuitable and the drilling difficult and no production was obtained except in Ventura County. Even there the production was of little importance commercially, and not until the early '80s did it become sufficient to again attract attention. In 1888 the production for the State had reached a total of about 700,000 bbl. per year, practically all light oil produced in Ventura County, Pico Canyon, Los Angeles County and in the Puente Hills. The production of petroleum attained the dignity of an industry in 1895 when the Los Angeles City and Coalinga fields were discovered. The subsequent development has been remarkable, and in 20 years the production has increased from 1,000,000 to 100,000,000 bbl. per year. The refining industry has kept pace with the production of oil. The Pacific Coast Oil Co., the predecessor of the Standard Oil Co. of California, was the virtual pioneer refining company of the State, having built a refinery at Alameda about 1880. When purchased by the Standard, about 1902, it was dismantled and the refinery at Point Richmond was built. The Richmond refinery is now one of the largest in the world, having a capacity in excess of 60,000 bbl. per day. A small refinery was built by the Union Oil Co. at Santa Paula in the early days of the industry and later many asphalt refineries were in operation in Southern California. The Pacific Coast Oil Co. was then, as has been its successor, the Standard Oil Co. of California, the principal refiner and marketer of light products, the most valuable of which was kerosene.

Jan 6, 1916

By H. Huang, R. N. Gow

"In Part I, Gibbs’ phase rule was applied to mass-balanced EH-pH diagrams for the Cu-As-S-H2O system. The diagrams were generated using the stoichiometry of enargite as a basis. In this study, the calculations were expanded to cover the stoichiometries of three other Cu-As-S minerals – tennantite, sinnerite and lautite – and compared with enargite. Stability regions within the resulting EH-pH diagrams were found to change with stoichiometry such that a particular mineral would predominate if its stoichiometry was used in the calculation. Solution speciation was also found to vary, with thioarsenate being the best example. This stoichiometric effect helps to explain results reported in the literature and would be difficult to realize if it were not for mass-balanced calculations. IntroductionA comprehensive thermodynamic review has been conducted on the aqueous copper-arsenic-sulfur (Cu- As-S) system (Gow et al., 2014, 2015a, 2016b; Gow, Huang and Young, 2016c). Data on the free energies of more than 100 species were collected from various authors, and thermodynamic databases collated to produce mass-balanced EH-pH diagrams using the thermodynamic equilibrium calculation software STABCAL (Huang, 2014). The full database is listed and discussed in Gow et al. (2015a). Diagrams were generated for enargite and confirmed with Raman spectroscopy using bulk mineral electrodes in order to identify reactions spectroelectrochemically. Theoretical calculations agreed well with the experimental results under alkaline conditions (Gow et al., 2015a), acid conditions (Gow et al., 2014) and alkaline sulfide leaching conditions (Gow et al., 2015b).In the present study, additional mass-balanced EH-pH diagrams were generated by changing the Cu-As-S stoichiometry from enargite (Cu3AsS4) to tennantite (Cu12As4S13), sinnerite (Cu6As4S9) and lautite (CuAsS). Regions for the thermodynamically stable species were shown to change with the four different mineral compositions. Potential leach conditions, both for co-dissolution and selective dissolution techniques, were examined for differences in predominant species according to changing copper-to-arsenic ratios, sulfur compositions and sulfur oxidation states."

Jan 1, 2016

By R. B. Rosene, G. L. Foster, A. R. Hendrickson

he properties of some of the common fracturing oils, such as sand-falling rate, fluid loss and viscasity, are a function of the three major constituents of the oil. These are: asphaltic material, parafin waxes and a base oil. The base oil can be either high or low viscosity. Asphaltic material increases viscosity by thickening the oil, decreasing the rate of fall of sand through the oil. at temperatures up to 200" F. When large arnorrnts of parafin wax are present, much of the wax i.s not dissolved, but is present in the form of rnicroscopic crystals. 7'his, of course is limited to temperatures below the melting points of waxe.s. As a result, parafin waxes clo not function primarily as thickener.7, but rother as bullting materials. The functiori of wax, without asphaltic material, in a low viscosity base oil is uniquely unlike that of wax with asphalt coexistent in the oil. The resulting difierence in wax crystal size governs the sand-falling rate to a large extent. An ideal type of fracturing oil is one containing neither asphalt nor waxes. In such cases, the viscosity and resulting low sand-falling rate are apparently due to soluble resin- ous hydrocarbons, which are compatible with formation oils. INTRODUCTION Since the introduction of hydraulic fracturing as a method of stimulating production from oil and gas wells, a variety of fluids have been employed to open the fractures and carry the propping agent. Such fluids include gels, emulsions, and oils. In the latter category, the use of refined oils has increased tremendously, and it is probably safe to assume that such oils represent more than one-half of the total fluid used in fracturing. The general acceptance of refined oils for fracturing can be accounted for on the basis of their relatively low cost and general applicability. To minimize transportation costs, such refined oils are generally obtained within the local areas of operation. As a result there are several kinds of oil used in different areas, with a wide variation in the basic composition. These types may vary from a fair grade of lubricating stock to a highly viscous cut-back asphalt. or road oil. Originally, little attention was paid to the composition of the oils used for fracturing, and any oil which would carry sand was considered satisfactory. Recently, however, service companies and well operators have become more concerned with the type of oils used for fracturing. With this in mind, the present work was undertaken to evaluate and compare many widely used fracturing oils to determine which constituents were most desirable for fracturing purposes. Some of the important properties of fracturing fluids are sand-falling rate, viscosity, and fluid loss. Other properties, that are actually of no less importance, include flash point, pour point, emulsifying tendencies with formation brines, and compatability with the formation oils. This discussion has been limited, however, to the first mentioned properties in order to give some idea of the general composition of the refined oils, how they function, and why. PROPERTIES OF FRACTURING OILS The properties of fracturing oils are a function of the three major constituents of the oil. These may be designated as: (1) asphaltic material, (2) paraffin waxes and (3) a base oil, which may be of either high or low viscosity. The asphaltic material clas-

Jan 1, 1956

By Michael D. Dunn

The Bureau of Mines evaluated a quartz schist formation within the Blue Joint Wilderness Study Area which was identified as having a "high potential" for copper-silver-cobalt-barium resources. Stratiform and remobilized copper occurs near, and bedded barite within, the study area. In addition, the black to gray Proterozoic quartz schist may correlate with the Yellowjacket Formation which contains cobalt-copper-gold-silver deposits at Blackbird, ID, about 30 miles to the south. Eighty soil and 43 rock samples collected across the quartz schist formation were analyzed for gold, silver, copper, cobalt, and barium. During the reconnaissance and sampling, particular attention was given to looking for malachite (copper carbonate) and erythrite (cobalt arsenate, also known as "cobalt bloom"). The sample analyses and geology in this localized area do not provide enough evidence to support the "high potential" designation for copper-silver-cobalt resources. Barium potential still appears high, however.

Jan 1, 1987

By Guangliang Wu, Dongchang Huang, Xinbin Liu

Oxidation Kinetics of SPHC was analyzed by TGA, and the curve of oxidation weight gain with different temperature was acquired. It is found that, when the oxidation temperature is between 500 and 600 , all the curves are linear; when the oxidation temperature is above 700 , the curves are close to parabolic. At the temperature of 900 , the oxidation weight gain increases dramatically. The TGA results indicate that the activation energy of SPHC steel is 146.19 kJ/mol at the temperature of 500 900 , and an oxidation kinetic model was set up for variable temperature. Based on the temperature change during rolling process, numerical simulation of oxide scales evolution was carried out for SPHC steel, and the simulation result agreed well with measured ones. It can provide a basis for estimating the scale growth and controlling the temperature on site.

Jan 1, 2016

Universal Resources Ltd has acquired a large portfolio of high quality exploration projects in two of Australia's most prospective regions for base and precious metal exploration: the Mt Isa Inlier (the Mt Isa-Cloncurry area) of North West Queensland, and the southern Lachlan Fold Belt in New South Wales. Drilling techniques commonly employed by the company for mineral exploration include diamond core drilling, air core drilling, reverse circulation (RC) drilling, and rotary air blast (RAB) drilling. Using examples from these two regions, each drilling technique is briefly described and compared, with particular reference to the specific advantages and disadvantages of each method for: sampling size, sample representivity, recovery, integrity and potential contamination. The applicability and implications of the different drilling techniques described for subsequent mineralogical and metallurgical evaluation work are discussed.

Mar 1, 2010

By Xing Yang, Zhen Peng, Guangwen Zhang, Haifeng Wang, Yaqun He

"Triboelectric separation of ilmenite ore based on the tribocharge differences between ilmenite and gangue minerals was conducted in this study. Triboelectric characteristics of ilmenite and its associated minerals were studied using polyvinyl chloride (PVC), pentatricopeptide repeats (PPR), copper, polymethyl methacrylate (PMMA), stainless steel (SS), teflon and quartz glass (QG) tribochargers in lab triboelectric unit. Results demonstrated that the ilmenite particles tribocharged positively while gangue minerals tribocharged negatively using PVC as tribocharger. The particle size also has a significant effect on tribocharge, and the -0.125+0.074 mm is the optimal size fraction of triboelectric separation. Charge-mass ratios of minerals increase with the increases of tribocharging length, but the increasing rate gradually reduce. At 1.5 m tribocharging length, charge-mass ratios of ilmenite, quartz, feldspar and mica are up to 6.07 nC/g, -6.05 nC/g, -4.30 nC/g and -4.56 nC/g, respectively. Based on the triboelectric characteristics of each mineral, triboelectric separation of ilmenite was conducted, and the grade of ilmenite ore increased from 15.47% to 28.40%. INTRODUCTION As a transition metal titanium plays an irreplaceable role in medical, aerospace and materials due to its light weight, high strength and corrosion resistance. Pure titanium dioxide is an excellent white pigment and is widely applied in industries of paint and textile. Ilmenite is the main raw material for titanium industry. For the beneficiation of ilmenite, series methods have been proposed, such as the application of dry magnetic and wet gravity separations to separate the ilmenite from the zircon and rutile. Electrostatic separation is extensively used in the beneficiation of heavy mineral sands for the recovery of rutile, zircon and ilmenite while flotation is used to separate fine ilmenite (Mehdilo et al., 2014; Fan et al., 2014). Compared with flotation and gravity separation, electrostatic separation does not consume water, and native properties of materials will not be changed and energy consumption will be reduced (Wang et al., 2014). Thus, the wide application of electrostatic separation and other dry separation methods is a trend in separation and purification industry, especially in water-scarce areas."

Jan 1, 2018

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