• Journal of Electrochemical Science and Technology
• /
• v.2 no.2
• /
• pp.76-84
• /
• 2011

Potentiostatic oxidation of Pb-1.7%Sb alloy used in the manufacture of grids of lead-acid batteries over the potential range from -1.0V to 2.3V in 5M $H_2SO_4$ in the absence and the presence of 0.4M $H_3PO_4$ and the self-discharge characteristics of the oxide layer formed is studied by electrochemical impedance spectroscopy (EIS). Depending on the potential value, sharp variations in resistance and capacitance of the alloy are recorded during the oxidation and they can be used for identification of the various substances involved in passive layer. Addition of $H_3PO_4$ is found to deteriorate the insulating properties of the passive layer by the retardation of the formation of $PbSO_4$. $H_3PO_4$ completely inhibits the current and impedance fluctuations recorded in $H_3PO_4$-free solutions in the potential range 0.5 V-1.7 V. These fluctuations are attributed to the occurrence of competitive redox processes that involve the formation of $PbSO_4$, $PbOSO_4$, PbO and $PbO_2$ and the repeated formation and breakdown of the passive layer. Self-discharge experiments indicate that the amount of $PbO_2$ formed in the presence of $H_3PO_4$ is lesser than in the $H_3PO_4$-free solutions. The start of transformation of $PbSO_4$ into $PbO_2$ is greatly shortened. $H_3PO_4$ facilitates the diffusion process of soluble species through the passive layer ($PbSO_4$ and basic $PbSO_4$) but impedes the diffusion process through $PbO_2$.

• Corrosion Science and Technology
• /
• v.7 no.2
• /
• pp.69-76
• /
• 2008

Common methods for large scale hydrogen production, such as steam reforming and coal gasification, also involve production of carbonaceous gases. It is therefore necessary to handle process gas streams involving various mixtures of hydrocarbons, $H_2$, $H_2O$, CO and $CO_2$ at moderate to high temperatures. These gases pose a variety of corrosion threats to the alloys used in plant construction. Carbon is a particularly aggressive corrodent, leading to carburisation and, at high carbon activities, to metal dusting. The behaviour of commercial heat resisting alloys 602CA and 800, together with that of 304 stainless steel, was studied during thermal cycling in $CO/CO_2$ at $650-750^{\circ}C$, and also in $CO/H_2/H_2O$ at $680^{\circ}C$. Thermal cycling caused repeated scale separation, which accelerated chromium depletion from the alloy subsurface regions. The $CO/H_2/H_2O$ gas, with $a_C=2.9$ and $p(O_2)=5\times10^{-23}$ atm, caused relatively rapid metal dusting, accompanied by some internal carburisation. In contrast, the $CO/CO_2$ gas, with $a_C=7$ and $p(O_2)=10^{-23}-10^{-24}$ atm caused internal precipitation in all three alloys, but no dusting. Inward diffusion of oxygen led to in situ oxidation of internal carbides. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.

• Environmental Engineering Research
• /
• v.25 no.2
• /
• pp.186-196
• /
• 2020

Pillared clays with Zr and Fe/Cu/Zr polycations have been prepared from natural clays found in large deposits of Kazakhstan and assessed as catalysts for the catalytic wet peroxide oxidation (CWPO), using 4-nitrophenol (4-NP) as model compound. The performance of the catalysts was followed by measuring the concentration of 4-NP, H₂O₂ and the total organic carbon (TOC), considering C_4-NP = 5 g L^-1, $C_{H_2O_2}$ = 17.8 g L^-1, C_cat = 2.5 g L^-1, initial pH = 3.0 and T = 50℃. At those selected conditions, the pillared clays showed higher activity than natural clays in the CWPO of 4-NP. The conversion of the model pollutant was complete when Fe/Cu/Zr-PILCs were used, with the TOC removal reaching 78.4% after 24 h with the best Fe/Cu/Zr-PILC. The H₂O₂, 4-NP and TOC time-evolution was well described by a kinetic model based on TOC lumps in three blocks, considering the initial TOC (corresponding to 4-NP), the production of oxidizable intermediates and the formation of refractory products.

• Journal of Environmental Science International
• /
• v.20 no.2
• /
• pp.251-260
• /
• 2011

$TiO_2$- and $SiO_2$-supported $Co_3O_4$, Pt and $Co_3O_4$-Pt catalysts have been studied for CO and $C_3H_8$ oxidations at temperatures less than $250^{\circ}C$ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at $350^{\circ}C$ and reduction at $400^{\circ}C$ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/$TiO_2$ catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported $Co_3O_4$-only catalysts are very active for CO oxidation even at $100^{\circ}C$, but the use of $TiO_2$ as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for $Co_3O_4$-Pt catalysts. Based on activity profiles of CO oxidation at $100^{\circ}C$ over a physical mixture of supported Pt and $Co_3O_4$ after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for $C_3H_8$ oxidation at $250^{\circ}C$ with a Pt-exchanged $SiO_2$ catalyst, this study may offer an useful approach to substitute $Co_3O_4$ for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.

• Journal of Soil and Groundwater Environment
• /
• v.18 no.4
• /
• pp.50-57
• /
• 2013

For the last couple of decades, the Fenton (-like) systems have been extensively studied for oxidation of organic contaminants in water. Recently, zero-valent iron (ZVI) has received attention as a Fenton catalyst as well as a reducing agent capable of producing reactive oxidants from oxygen. In this study, the ZVI-based Fenton reaction was assessed for the oxidative degradation of phenol using $ZVI/O_2$, $ZVI/H_2O_2$, ZVI/Oxalate/$O_2$ and hv/ZVI/Oxalate/$O_2$ systems. Reaction parameters such as pH and reagent dose (e.g., ZVI, $H_2O_2$, and oxalate) were examined. In the presence of oxalate (ZVI/Oxalate/$O_2$ and hv/ZVI/Oxalate/$O_2$ systems), the degradation of phenol was greatly enhanced at neutral pH values. It was found that ZVI accelerates the Fenton reaction by reducing Fe(III) into Fe(II). The conversion of Fe(III) into Fe(II) by ZVI was more stimulated at acidic pH than at near-neutral pH values.

• Economic and Environmental Geology
• /
• v.53 no.6
• /
• pp.687-694
• /
• 2020

Two oxidizing agents (KMnO4, H2O2), and one neutralizing agent (NaOH) were applied to evaluate Mn removal in mine drainage. A Mn2+ solution and artificial mine drainage were prepared to identify the Fe2+ influence on Mn2+ removal. The initial concentrations of Mn2+ and Fe2+ were 0.1 mM and 1.0 mM, respectively. The injection amount of oxidizing and neutralizing agents were set to ratios of 0.1, 0.67, 1.0, and 2.0 with respect to the Mn2+ mole concentration. KMnO4 exhibited a higher removal efficiency of Mn2+ than did H2O2 and NaOH, where approximately 90% of Mn2+ was removed by KMnO4. A black MnO2 was precipitated that indicated the oxidation of Mn2+ to Mn4+ after an oxidizing agent was added. In addition, MnO2 (pyrolusite) is a stable precipitate under pH-Eh conditions in the solution. However, relatively low removal ratios (6%) of Mn2+ were observed in the artificial mine drainage that included 1.0 mM of Fe2+. The rapid oxidation tendency of Fe2+ as compared to that of Mn2+ was determined to be the main reason for the low removal ratios of Mn2+. The oxidation of Fe2+ showed a decrease of Fe concentration in solution after injection of the oxidizing and neutralizing agents. In addition, Mn7+ of KMnO4 was reduced to Mn2+ by Fe2+ oxidation. Thus, the concentrations of Mn increased in artificial mine drainage. These results revealed that the oxidation method is more effective than the neutralization method for Mn removal in solution. It should also be mentioned that to achieve the Mn removal in mine drainage, Fe2+ removal must be conducted prior to Mn2+ oxidation.

• Journal of Korean Society on Water Environment
• /
• v.25 no.1
• /
• pp.90-95
• /
• 2009

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by advanced oxidation process (i.e., UV process). The experiments were performed with various pH, initial concentration, UV intensity, and addition of $H_2O_2$ or $TiO_2$ on UV process. The results showed that the direct UV photolysis was the most effective treatment method. The lower pH, intial concentration and higher intensity of UV stimulated higher NDMA removal. However, addition of oxidant ($H_2O_2$, $TiO_2$) slows down photochemical treatment of NDMA since the oxidant can filter out the UV light and block it to reach the NDMA molecules. Dimethylamine (DMA) and nitrite were found to be a major byproduct from NDMA oxidation. To evaluate the chronic toxicity effects of UV-treated NDMA on the growth of microalgae, "Skeletonema costatum", was studied as long term experiments. Results demonstrated that after the 13 days exposure the chronic toxicity was decreased about 15% with application of UV process on NDMA degradation.

• Journal of Korean Society of Environmental Engineers
• /
• v.28 no.12
• /
• pp.1323-1330
• /
• 2006

In this study, five different odor causing compounds in the Nakdong river and rapid sand filtered waters were treated by oxidation from $O_3/H_2O_2$ process. In addition, the change in BDOC formation by the $O_3/H_2O_2$ process was also investigated for considering this advanced oxidation Process as a pre-treatment to the BAC treatment process. The experimental result showed that the removal efficiency of geosmin was higher with the use of 5 mg/L of $O_3$ and 0.2 mg/L of $H_2O_2$ than with the use of 20 mg/L of $O_3$ alone for the sand filtered water. And in general, the removal efficiency of geosmin in raw water was $12{\sim}27%$ lower than the one in sand filtered water. In sand filtered water. the removal efficiencies of geosmin and IPMP decreased when $H_2O_2/O_3$ ratio increases above the optimum ratio. The optimum ratio of $H_2O_2/O_3$ dose was $0.5{\sim}1.0$ for geosmin and $0.2{\sim}1.0$ for IPMP. However, the optimum ratio of $H_2O_2/O_3$ in raw water remove geosmin appealed to $1.0{\sim}3.0$. According to the experimental results for the removal of 5 different odor causing compounds under varied $O_3$ doses, the removal efficiency of IPMP was the highest with 60% and, in overall, $O_3/H_2O_2$ process showed higher removal efficiency than $O_3$ alone process. The BDOC formation by the $O_3/H_2O_2$ process increased from $0.1{\sim}0.25$ to $0.19{\sim}0.34$ comparing to $O_3$ process alone. Therefore, it is concluded that the advanced oxidation process with $O_3/H_2O_2$ can be used as a pretreatment to the BAC treatment process.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 2013.05a
• /
• pp.53-54
• /
• 2013

Nano-multilayered CrAlSiN films consisting of crystalline CrN nanolayers and amorphous AlSiN nanolayers were deposited by cathodic arc plasma deposition. Their oxidation characteristics were studied between 600 and $1000^{\circ}C$ for up to 70 h in air. During their oxidation, the amorphous AlSiN nanolayers crystallized. The formed oxides consisted primarily of $Cr_2O_3$, ${\alpha}-Al_2O_3$, $SiO_2$. The outer $Al_2O_3$ layer formed by outward diffusion of Al ions. Simultaneously, an inner ($Al_2O_3$, $Cr_2O_3$)-mixed layer formed by the inward diffusion of oxygen ions. $SiO_2$ was present mainly in the lower part of the oxide layer due to its immobility. The CrAlSiN films displayed good oxidation resistance, owing to the formation of oxide crystallites of $Cr_2O_3$, ${\alpha}-Al_2O_3$, and amorphous $SiO_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2000.07a
• /
• pp.946-949
• /
• 2000

Amorphous MnO$_2$$.$ nH$_2$O in 1M KOH aqueous electrolyte proves to be an excellent electrode for a faradic electrochemical capacitor cycled between -0.5 and +1.0 versus Ag/AgCl. In order to observe morphology and crystalline structure of MnO$_2$powder, we analyzed it by XRD and SEM. The effect of oxidation treatment on MnO$_2$electrode was observed by different oxidation voltages. A maximum capacitance of 364F/g was obtained by 1.1V oxidation treatment. This capacitance was attributed solely to a surface redox mechanism