A study of slag corrosion of oxides and oxide-carbon refractories during steel refining

The use of ceramic material as refractories in the manufacturing industry is a common practice worldwide. During usage, for example in the production of steel, these materials do experience severe working conditions including high temperatures, low pressures and corrosive environments. This results in lowered service lives and high consumptions of these materials. This, in turn, affects the productivity of the whole steel plant and thereby the cost. In order to investigate how the service life can be improved, studies have been carried out for refractories used in the inner lining of the steel ladles. More specifically, from the slag zone, where the corrosion is most severe. By combining thermodynamic simulations, plant trails and post-mortem studies of the refractories after service, vital information about the behaviour of the slagline refractories during steel refining and the causes of the accelerated wear in this ladle area has been achieved. The results from these studies show that the wear of the slagline refractories of the ladle is initiated at the preheating station, through reduction-oxidation reactions. The degree of the decarburization process is mostly dependent on the preheating fuel or the environment. For refractories without antioxidants, refractory decarburization is slower when coal gas is used in ladle preheating than when a mixture of oil and air is used. In addition, ladle preheating of the refractories without antioxidants leads to direct wear of the slagline refractories. This is due to the total loss of the matrix strength, which results in a sand-like product. Thermal chemical changes that take place in the slagline refractories are due to the MgO-C reaction as well as the formation of liquid phases from impurity oxides. In addition, the decrease in the system pressure during steel refining makes the MgO-C reaction take place at the steel refining temperatures. This reduces the refractory’s resistance to corrosion. This is a serious problem for both the magnesia-carbon and dolomite-carbon refractories. The studies of the reactions between the slagline refractories and the different slag compositions showed that slags rich in iron oxide lead mostly to the oxidation of carbon/graphite in the carbon-containing refractories. This leads to an increased porosity and wettability and therefore an enhanced penetration of slag into the refractory structure. If the slag contains high contents of alumina and or silica (such as the steel refining slag), reactions between the slag components and the dolomite-carbon refractory are promoted. This leads to the formation of low-temperature melting phases such as calcium-aluminates and silicates. The state of these reaction products during steel refining leads to an accelerated wear of the dolomite-carbon refractory. The main products of the reactions between the magnesia-carbon refractory and the steel refining slag are MgAl2O4 spinels, and calcium-aluminates, and silicates. Due to the good refractory properties of MgAl2O4 spinels, the slag corrosion resistance of the magnesiacarbon refractory is promoted.

Use of a carbon paste electrode modified with spinel-type manganese oxide as a potentiometric sensor for lithium ions in flow injection analysis

A potentiometric sensor constructed from a mixture of 25% (m/m) spinel-type manganese oxide (lambda-MnO2), 50% (m/m) graphite powder and 25% (m/m) mineral oil is used for the determination of lithium ions in a flow injection analysis system. Experimental parameters, such as pH of the carrier solution, flow rate, injection sample volume, and selectivity for Li+ against other alkali and alkaline-earth ions and the response time of this sensor were investigated. The sensor response to lithium ions was linear in the concentration range 8.6 x 10(-5) - 1.0 x 10(-2) mol L-1 with a slope 78.9 +/- 0.3 mV dec(-1) over a wide pH range 7 - 10 (Tris buffer), without interference of other alkali and alkaline-earth metals. For a flow rate of 5.0 mL min(-1) and a injection sample volume of 408.6 muL, the relative standard deviation for repeated injections of a 5.0 x 10(-4) mol L-1 lithium ions was 0.3%.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GFAAS with transversely heated graphite atomizer and longitudinal zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)2 + Mg(NO3)2 as the chemical modifier. With 5 μg Pd + 3 μg Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400°C and 2100°C, respectively, and 20 μL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 -50.0 μg L-1 for As, Sb, Se; 10.0 - 100 μg L-1 for Cu; and 20.0 - 200 μg L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 μg L-1 As, 0.2 μg L-1 Cu, 0.6 μg L-1 Mn, 0.3 μg L-1 Sb, 0.9 μg L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 μg L-1, 1000 μg L-1, 2000 μg L-1, 5 μg L-1, and 50 μg L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mn, Sb, and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

Tin oxide based composites derived using electrostatic spray deposition technique as anodes for lithium-ion batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200, 250, 300 °C) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 °C deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 °C exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 °C showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2–74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Primary alkaline battery cathodes a three-scale model

A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

Purity evaluation and influence of carbon nanotube on carbon nanotube/graphite thermal stability

High resolution thermogravimetry has been used to evaluate the carbonaceous content in a commercial sample of single-walled carbon nanotube (SWNT). The content of SWNTs in the sample was found to be at least 77mass% which was supported by images obtained with scanning and transmission electron microscopies (SEM and TEM). Furthermore, the influence of SWNT addition on the thermal stability of graphite in mixtures of SWNT/graphite at different proportions was investigated. The graphite stability decreased with the increased of SWNT content in the overall range of composition. This behavior could be due to the close contact between these carbonaceous species as determined by SEM analysis.

Infrared and infrared emission spectroscopy of gallium oxide α-GaO(OH) nanostructures

Infrared spectroscopy has been used to study nano to micro sized gallium oxyhydroxide α-GaO(OH), prepared using a low temperature hydrothermal route. Rod-like α-GaO(OH) crystals with average length of ~2.5 μm and width of 1.5 μm were prepared when the initial molar ratio of Ga to OH was 1:3. β-Ga2O3 nano and micro-rods were prepared through the calcination of α-GaO(OH) The initial morphology of α-GaO(OH) is retained in the β-Ga2O3 nanorods. The combination of infrared and infrared emission spectroscopy complimented with dynamic thermal analysis were used to characterise the α-GaO(OH) nanotubes and the formation of β-Ga2O3 nanorods. Bands at around 2903 and 2836 cm-1 are assigned to the -OH stretching vibration of α-GaO(OH) nanorods. Infrared bands at around 952 and 1026 cm-1 are assigned to the Ga-OH deformation modes of α-GaO(OH). A significant number of bands are observed in the 620 to 725 cm-1 region and are assigned to GaO stretching vibrations.