• Journal of the Korean Ceramic Society
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• v.47 no.1
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• pp.26-38
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• 2010

Degradation in Solid Oxide Fuel Cell performance can be ascribed to the following fundamental processes from the materials chemical point of view; that is, diffusion in solids and reaction with gaseous impurities. For SOFC materials, diffusion in solids is usually slow in operation temperatures $800\sim1000^{\circ}C$. Even at $800^{\circ}C$, however, a few processes are rapid enough to lead to some degradations; namely, Sr diffusion in doped ceria, cation diffusion in cathode materials, diffusion related with metal corrosion, and sintering of nickel anodes. For gaseous impurities, chromium containing vapors are important to know how the chemical stability of cathode materials is related with degradation of performance. For LSM as the most stable cathode among the perovskite-type cathodes, electrochemical reduction reaction of $CrO_3$(g) at the electrochemically active sites is crucial, whereas the rest of the cathodes have the $SrCrO_4$ formation at the point where cathodes meet with the gases, leading to rather complicated processes to the degradations, depending on the amount and distribution of reacted Cr component. These features can be easily generalized to other impurities in air or to the reaction of nickel anodes with gaseous impurities in anode atmosphere.

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.783-786
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• 2009

Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and ion chromatography(IC) were employed to analyze the thermal behavior of $Li_xCoO_2$ cathode material of lithium ion battery. The mass loss peaks appearing between 60 and 125 ${^{\circ}C}$ in TGA and the exothermic peaks with 4.9 and 7.0 J/g in DSC around 75 and 85 ${^{\circ}C}$ for the $Li_xCoO_2$ cathodes of 4.20 and 4.35 V cells are explained based on disruption of solid electrolyte interphase (SEI) film. Low temperature induced HF formation through weak interaction between organic electrolyte and LiF is supposed to cause carbonate film disruption reaction, $Li_2CO_3\;+\;2HF{\rightarrow}\;2LiF\;+\;CO_2\;+\;H_2O$. The different spectral DSC/TGA pattern for the cathode of 4.5 V cell has also been explained. Presence of ionic carbonate in the cathode has been identified by ion chromatography and LiF reported by early researchers has been used for explaining the film SEI disruption process. The absence of mass loss peak for the cathode washed with dimethyl carbonate (DMC) implies ionic nature of the film. The thermal behavior above 150 ${^{\circ}C}$ has also been analyzed and presented.

• Ceramist
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• v.23 no.2
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• pp.200-210
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• 2020

Supported catalysts are at the heart of manufacturing essential chemical, agricultural and pharmaceutical products. While the longevity of such systems is critically hinged on the durability of metal nanoparticles, the conventional deposition/dispersion techniques are difficult to enhance the stability of the metal nanoparticles due to the lack of control over the interaction between metal-support. Regarding this matter, ex-solution has begun to be recognized as one of the most promising methodologies to develop thermally and chemically robust nanoparticles. By dissolving desired catalysts as a cation form into a parent oxide, fine and uniformly distributed metal nano-catalysts can be subsequently grown in situ under reductive heat treatment, which is referred to ex-solution. Over the several years, ex-solved analog has resulted in tremendous progress in the chemical-electrochemical applications due to the exceptional robustness coupled with ease synthesis. Herein, we describe the ex-solution process in detail which therein introducing the unique characteristics of ex-solved particles that distinguish them from conventionally dispersed nanoparticles. We then go through the history of science regarding the ex-solution phenomena and summarize several major research achievements which embrace the ex-solved nanoparticles to markedly promote the catalytic performances. In conclusion, we address the remaining challenges and the future perspectives of this rapidly growing field.

• Bulletin of the Korean Chemical Society
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• v.11 no.6
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• pp.521-527
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• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

• Korean Journal of Metals and Materials
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• v.49 no.12
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• pp.937-944
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• 2011

Studies have been carried out in order to reduce fuel-cladding chemical interaction (FCCI) behavior of metallic fuel in sodium-cooled fast reactors (SFR) using an electroplating technique. A $20{\mu}m$ thick Cr layer has been plated by the electrochemical method in the Sargent bath over the HT9 (12Cr-1Mo) clad material and diffusion couple tests of the U-10Zr metallic fuel as well as the rare earth alloy (70Ce-29La) have been conducted. The results show that the Cr plating can prevent FCCI behavior along the fuel-clad interface. However, cracks developed through the thickness during plating, which resulted in the migration of some fuel constituents. Variation of bath temperature, application of pulse current, and post heat treatment have been conducted to control such cracks. We found out that some conditions like the pulse current and the post heat treatment enhanced the layer property by reducing the internal cracks and improving the diffusion couple test.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.29 no.5C
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• pp.217-228
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• 2009

In case of application of electrophoresis method for leakage restoration of waste impoundment, main points of consideration were to evaluate the mobility of clay particles by electrophoretic force and capacity of leakage repair in leachate electrolyte system contained with various chemical species. However, the flocculation phenomena of clay particles induced by electrochemical interaction between various chemical species and clay particles would cause the big problems in electrophoresis method. Therefore, a series of laboratory tests such as one-dimensional electrophoresis and gravitational experiments were carried out in order to identify the specific chemical species affected flocculation of clay particles and the range of chemical concentration in leachate. In addition, the characteristics of clay particle behavior with chemical species and concentration range in leachate were analized using the concept of the settling velocity, zeta potential, and electrophoretic velocity.

• Journal of the Korean Electrochemical Society
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• v.10 no.2
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• pp.132-140
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• 2007

The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

• Restorative Dentistry and Endodontics
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• v.32 no.4
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• pp.377-384
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• 2007

Present tooth bonding system can be categorized into total etching bonding system (TE) and self-etching boding system (SE) based on their way of smear layer treatment. The purposes of this study were to compare the effectiveness between these two systems and to evaluate the effect of number of themocycling on microleakage of class V composite resin restorations. Total forty class V cavities were prepared on the single-rooted bovine teeth and were randomly divided into four experimental groups: two kinds of bonding system and another two kinds of thermocycling groups. Half of the cavities were filed with Z250 following the use of TE system, Single Bond and another twenty cavities were filled with Metafil and AQ Bond, SE system. All composite restoratives were cured using light curing unit (XL2500, 3M ESPE, St. Paul, MN, USA) for 40 seconds with a light intensity of $600mW/cm^2$. Teeth were stored in distilled water for one day at room temperature and were finished and polished with Sof-Lex system. Half of teeth were thermocycled 500 times and the other half were thermocycled 5,000 times between $5^{\circ}C$ and $55^{\circ}C$ for 30 second at each temperature. Teeth were isolated with two layers of nail varnish except the restoration surface and 1 mm surrounding margins. Electrical conductivity (${\mu}A$) was recorded in distilled water by electrochemical method. Microleakage scores were compared and analyzed using two-way ANOVA at 95% level. From this study, following results were obtained: There was no interaction between variables of bonding system and number of thermocycling (p = 0.485). Microleakage was not affected by the number of thermocycling either (p = 0.814). However, Composite restoration of Metafil and AQ Bond, SE bond system showed less microleakage than composite restoration of Z250 and Single Bond, TE bond system (p = 0.005).

• Journal of Information Display
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• v.12 no.3
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• pp.145-152
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• 2011

Since the discovery of fullerenes as a class of nanostructure compounds, many potential applications have been suggested for their unusual structures and properties. The isolated pentagon rule (IPR) states that all pentagonal carbon rings are isolated in the most stable fullerene. Fullerenes $C_n$ are a class of spherical carbon allotrope group with unique properties. Electron transfer between fullerenes and other molecules is thought to involve the transfer of electrons between the molecules surrounding the fullerene cage. One class of electron transfer molecules is the methanofullerene derivatives ([6,6]-phenyl $C_{61}$-butyric acid methyl ester (PCBM), 4-(2-ethylhexyloxy)-[6,6]-phenyl $C_{61}$-butyric acid methyl ester (p-EHO-PCBM), and 4-(2-ethylhexyloxy)-[6,6]-phenyl $C_{61}$-butyric acid (p-EHO-PCBA), 10-12). It has been determined that $C_{60}$ does not obey IPR. Supramolecular complexes 1-9 and 10-12 are shown to possess a previously unreported host.guest interaction for electron transfer processes. The unsaturated, cis-geometry, thiocrown ethers, (1-9) (described as [X-UT-Y], where X and Y indicate the numbers of carbon and sulfur atoms, respectively), are a group of crown ethers that display interesting physiochemical properties in the light of their conformational restriction compared with a corresponding saturated system, as well as the sizes of their cavities. Topological indices have been successfully used to construct mathematical methods that relate structural data to various chemical and physical properties. To establish a good relationship between the structures of 1-9 with 10-12, a new index is introduced, ${\mu}_{cs}$. This index is the ratio of the sum of the number of carbon atoms ($n_c$) and the number of sulfur atoms ($n_s$) to the product of these two numbers for 1-9. In this study, the relationships between this index and oxidation potential ($^{ox}E_1$) of 1-9, as well as the first to third free energies of electron transfer (${\Delta}G_{et(n)}$, for n = 1-3, which is given by the Rehm-Weller equation) between 1-9 and PCBM, p-EHO-PCBM, and p-EHO-PCBA (10-12) as [X-UT-Y]@R(where R is the adduct PCBM, p-EHO-PCBM, and p-EHO-PCBA group) (13-15) supramolecular complexes are presented and investigated.

• Analytical Science and Technology
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• v.5 no.3
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• pp.239-247
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• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.