• Korean Chemical Engineering Research
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• v.51 no.6
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• pp.700-708
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• 2013

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. Pyroprocessing has been developed with the dry technologies which are performed under high temperature conditions excluding any aqueous processes. Pyro-processes which are based on the electrochemical principles require pretreatment processes and a voloxidation process is considered as a pretreatment step for an electrolytic reduction process. Various kinds of gas conditions are applicable to the voloxidation process and the understanding of Cs behavior during the process is of importance for the analyses of waste characteristics and heat load on the overall pyroprocessing. In this study, the changes of chemical compounds with the gas conditions were calculated by analyzing gas-solid reaction behavior based on the chemical equilibria on a Cs-Te-O system. $Cs_2TeO_3$ and $Cs_2TeO_4$ were selected after a Tpp diagram analysis and it was confirmed that they are relatively stable under oxidizing atmospheres while it was shown that Cs and Te would be removed by volatilization under reducing atmosphere at a high temperature. This work provided basic data for predicting Cs behavior during the voloxidation process at which compounds are chemically distributed as the first stage in the pyroprocessing and it is expected that the results would be used for setting up material balances and related purposes.

• Journal of Preventive Medicine and Public Health
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• v.35 no.3
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• pp.229-235
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• 2002

Objectives : To evaluate the effects on the formation of benzidine-hemoglobin, and benzidine metabolite-hemoglobin adducts, caused by pretreatment with the known xenobiotic metabolism effectors, ethanol and phenobarbital, in rats administered Direct Black 38 dye. Methods : The experimental rats were divided into three groups: a control group, an ethanol group and a phenobarbital group. Rats were pretreated with ethanol (1g/kg) or phenobarbital (80mg/kg) 24 hours prior to the oral administration of Direct Black 38 (0.5mmol/kg), with the control group being administered the same amount of distilled water. Blood samples were obtained from the vena cava of 5 rats from each group prior to, and at 30 min, 3h, 5h, 9h, 12h, 24h, 48h, 72h, 96h, and 144h following the oral administration of Direct Black 38. Directly after sampling the blood was separated into hemoglobin and plasma, with the adducts being converted into aromatic amines by basic hydrolysis. Hydrolyzed benzidiene, monoacetylbenzidine and 4-aminobiphenyl were analyzed by reverse-phase liquid chromatography with an electrochemical detector, The quantitative amount of the metabolites was expressed by the hemoglobin binding index (HBI). Results : In the ethanol group, benzidine-, monoacetylbenzidine-, and 4-aminobiphenyl-HBI were increased to a greater extent than those in the control group. These results were attributed to the ethanol inducing N-hydrgxylation, which is related to the formation of the hemoglobin adduct, In the phenobarbital group, all the HBIs, with the exception of the benzidine-HBI, were increased to a greater extent than those of the control group. These results were attributed to the phenobarbital inducing N-hydroxylation related to the formation of the hemoglobin adduct. The N-acetylation ratio was only increased with the phenobarbital pretreatment due to the lower benzidine-HBI of the phenobarbital group compared to these of the control and ethanol groups. The N-acetylation ratios for all groups were higher than f for the duration of the experimental period. Although the azo reduction was unaffected by the ethanol, it was inhibited by the phenobarbital, The ratio of the benzidine-HBI in the phenobarbital group was lower than those of the ethanol the control groups for the entire experiment. Conclusion : Our results indicate that both ethanol and phenobarbital increase the formation of adducts by the induction of N-hydroxylation, but also induced N-acetylation. Phenobarbital decreased the formation of benzidine-HBI due to the decrease of the azo reduction. These results suggest that the effects or ethanol and phenobarbital need to be considered in the biochemical monitoring of Direct Black 38.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

• Journal of the Korean Electrochemical Society
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• v.22 no.3
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• pp.128-137
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• 2019

A lithium is the lightest metal on the earth. It has some attractive characteristics as a negative electrode material such as a low reduction potential (-3.04 V vs. SHE) and a high theoretical capacity ($3,860mAh\;g^{-1}$). Therefore, it has been studied as a next generation anode material for high energy lithium batteries. The thin lithium electrode is required to maximize the efficiency and energy density of the battery, but the physical roll-press method has a limitation in manufacturing thin lithium. In this study, thin lithium electrode was fabricated by electrodeposition under various conditions such as compositions of electrolytes and the current density. Deposited lithium showed strong relationship between process condition and its characteristics. The concentration of electrolyte affects to the shape of deposited lithium particle. As the concentration increases, the shape of particle changes from a sharp edged long one to a rounded lump. The former shape is favorable for suppressing dendrite formation and the elec-trode shows good stripping efficiency of 92.68% (3M LiFSI in DME, $0.4mA\;cm^{-2}$). The shape of deposited particle also affected by the applied current density. When the amount of current applied gets larger the shape changes to the sharp edged long one like the case of the low concentration electrolyte. The combination of salts and solvents, 1.5M LiFSI + 1.5M LiTFSI in DME : DOL [1 : 1 vol%] (Du-Co), was applied to the electrolyte for the lithium deposition. The lithium electrode obtained from this electrolyte composition shows the best stripping efficiency (97.26%) and the stable reversibility. This is presumed to be due to the stability of the surface film induced by the Li-F component and the DOL effect of providing film flexibility.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.3
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• pp.305-312
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• 2011

The use of a separator to control stack temperature in a molten carbonate fuel cell was studied by numerical simulation using a computational fluid dynamics code. The stack model assumed steady-state and constant-load operation of a co-flow stack with an external reformer at atmospheric pressure. Representing a conventional cell type, separators with two flow paths, one each for the anode and cathode gas, were simulated under conditions in which the cathode gas was composed of either air and carbon dioxide (case I) or oxygen and carbon dioxide (case II). The results showed that the average cell potential in case II was higher than that in case I due to the higher partial pressures of oxygen and carbon dioxide in the cathode gas. This result indicates that the amount of heat released during the electrochemical reactions was less for case II than for case I under the same load. However, simulated results showed that the maximum stack temperature in case I was lower than that in case II due to a reduction in the total flow rate of the cathode gas. To control the stack temperature and retain a high cell potential, we proposed the use of a separator with three flow paths (case III); two flow paths for the electrodes and a path in the center of the separator for the flow of nitrogen for cooling. The simulated results for case III showed that the average cell potential was similar to that in case II, indicating that the amount of heat released in the stack was similar to that in case II, and that the maximum stack temperature was the lowest of the three cases due to the nitrogen gas flow in the center of the separator. In summary, the simulated results showed that the use of a separator with three flow paths enabled temperature control in a co-flow stack with an external reformer at atmospheric pressure.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.134-134
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• 2010

Fuel cell is a device that directly converts chemical energy in the form of a fuel into electrical energy by way of an electrochemical reaction. In the anode for a high temperature fuel cell, nickel or nickel alloy has been used in consideration of the cost, oxidation catalystic ability of hydrogen which is used as fuel, electron conductivity, and high temperature stability in reducing atmosphere. Most MCFC stacks currently operate at an average temperature of $650^{\circ}C$. There is some gains with decreased temperature in MCFC to diminish the electrolyte loss from evaporation and the material corrosion, which could improve the MCFC life. However, operating temperature has a strong related on a number of electrode reaction rates and ohmic losses. Baker et al. reported the effect of temperature (575 to $650^{\circ}C$). The rates of cell voltage loss were 1.4mV/$^{\circ}C$ for a reduction in temperature from 650 to $600^{\circ}C$, and 2.16mV/$^{\circ}C$ for a decrease from 600 to $575^{\circ}C$. The two major contributors responsible for the change in cell voltage with reducing operation temperature are the ohmic polarization and electrode polarization. It appears that in the temperature range of 550 to $650^{\circ}C$, about 1/3 of the total change in cell voltage with decreasing temperature is due to an increase in ohmic polarization, and the electrode polarization at the anode and cathode. In addition, the oxidation reaction of hydrogen on an ordinary nickel alloy anode in MCFC is generally considered to take place in the three phase zone, but anyway the area contributing to this reaction is limited. Therefore, in order to maintain a high performance of the fuel cell, it is necessary to keep this reaction responsible area as wide as possible, that is, it is needed to keep the porosity and specific surface area of the anode at a high level. In this study effective anodes are prepared for low temperature MCFC capable of enhancing the cell performance by using zirconium hydride at least in part of anode material.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.87-87
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• 2010

Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

• Corrosion Science and Technology
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• v.13 no.2
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• pp.70-80
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• 2014

Duplex stainless steels with nearly equal fraction of the ferrite(${\alpha}$) phase and austenite(${\gamma}$) phase have been increasingly used for various applications such as power plants, desalination facilities due to their high resistance to corrosion, good weldability, and excellent mechanical properties. Hyper duplex stainless steel (HDSS) is defined as the future duplex stainless steel with a pitting resistance equivalent (PRE=wt.%Cr+3.3(wt.%Mo+0.5wt.%W)+30wt.%N) of above 50. However, when HDSS is welded with gas tungsten arc (GTA), incorporation of nitrogen in the Ar shielding gas are very important because the volume fraction of ${\alpha}$-phase and ${\gamma}$-phase is changed and harmful secondary phases can be formed in the welded zone. In other words, the balance of corrosion resistance between two phases and reduction of $Cr_2N$ are the key points of this study. The primary results of this study are as follows. The addition of $N_2$ to the Ar shielding gas provides phase balance under weld-cooling conditions and increases the transformation temperature of the ${\alpha}$-phase to ${\gamma}$-phase, increasing the fraction of ${\gamma}$-phase as well as decreasing the precipitation of $Cr_2N$. In the anodic polarization test, the addition of nitrogen gas in the Ar shielding gas improved values of the electrochemical parameters, compared to the Pure Ar. Also, in the erosion-corrosion test, the HDSS welded with shielding gas containing $N_2$ decreased the weight loss, compared to HDSS welded with the Ar pure gas. This result showed the resistance of erosion-corrosion was increased due to increasing the fraction of ${\gamma}$-phase and the stability of passive film according to the addition $N_2$ gas to the Ar shielding gas. As a result, the addition of nitrogen gas to the shielding gas improved the resistance of erosion-corrosion.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.369-377
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• 1982

The technique of combined-measurement of reflectance and ellipsometric parameters was used for studying the anodic film formed on nickel surface in basic solutions. An ellipsometer was automated for transient measurements by way of modulating the plane-polarized light with the Faraday effect. Surface film was formed electrochemically by applying a potential step from the reduction potential range to the passivation range on a polished, high-purity, polycrystalline nickel specimen. From that instant, the changes in the reflectance(r) and the ellipsometric parameters(${\Delta},{\Psi}$) of the surface film were recorded by the automatic ellipsometer. Three exact simultaneous equations including these optical signals, ${\Delta},{\Psi}$ and r were solved numerically with a computer in order to determine the optical properties, n, k, and the thickness, ${\tau}$, of the surface film. From the computed results which showed dependence on pH and time, it was found that passivation of nickel can be effectively attained by surface film thinner than $15{\AA}$ and this passivation film has a small optical absorption coefficient. It seemed that a high pH environment enhances the rate of passivation and is favorable for a denser structure of the surface film. The experimental evidence is in accordance with the hypothesis that the composition of the passive film can be approximated by $Ni(OH)_2$ in the early stage of passivation and that as time passes the composition changes partially toward that of NiO through dehydration.

• Journal of the Korean Applied Science and Technology
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• v.33 no.2
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• pp.352-360
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• 2016

The purpose of this study was to determine the electrochemical properties develop DSA electrode for sewage sludge solubilization. Using Ir as a main catalyst, the catalyst selected for the sewage sludge solubilization durability and proceeds to functional electrode suitable for sewage sludge electrolysis experiment were obtained the following results. Less mass reduction of the sintering temperature of the main catalyst, Ir coated electrodes, the endothermic reaction zone $300^{\circ}C$ to $500^{\circ}C$, which was selected from a range of experiments. The efficiency of the catalyst results came up to $350^{\circ}C$ best. Each Binder stars (Ta, Sn, W) in this experiment was the biggest catalyst efficiency at $350^{\circ}C$. Used as a binder, $TaCl_5$, $SnCl_4$, $WCl_6$ of the Ta and without affecting the other characteristics of the main catalyst than Sn, W. For the 50% $IrO_2$ electrode is 1.4 V (vs. Ag / AgCl) in a current of about $29mA/cm^2$ was caused to evaluate the effectiveness of the electrode.