• Journal of Hydrogen and New Energy
• /
• v.28 no.6
• /
• pp.610-617
• /
• 2017

This paper presents a study of the effect of thickness of porous Al-Ni electrodes, on the Hydrogen Evolution Reaction (HER) in alkaline media. As varying deposition time at 300 W DC sputtering power, the thickness of the Al-Ni electrodes was controlled from 1 to $20{\mu}m$. The heat treatment was carried out in $610^{\circ}C$, followed by selective leaching of the Al-rich phase. XRD studies confirmed the presence of $Al_3Ni_2$ intermetallic compounds after the heat treatment, indicating the diffusion of Ni from the Ni-rich phase to Al-rich phase. The porous structure of the Al-Ni electrodes after the selective leaching of Al was also confirmed in SEM-EDS analysis. The double layer capacitance ($C_{dl}$) and roughness factor ($R_f$) of the electrodes were increased for the thicker Al-Ni electrodes. As opposed to the general results in above, there were no further improvements of the HER activity in the case of the electrode thickness above $10{\mu}m$. This result may indicate that the $R_f$ is not the primary factor for the HER activity in alkaline media.

• Korean Chemical Engineering Research
• /
• v.53 no.4
• /
• pp.509-516
• /
• 2015

We investigated the reduction leaching process of manganese dioxide ore using black locust as reductant in sulfuric acid solution. The effect of parameters on the leaching efficiency of manganese was the primary focus. Experimental results indicate that manganese leaching efficiency of 97.57% was achieved under the optimal conditions: weight ratio of black locust to manganese dioxide ore (WT) of 4:10, ore particle size of $63{\mu}m$, $1.7mol{\cdot}L^{-1}\;H_2SO_4$, liquid to solid ratio (L/S) of 5:1, leaching time of 8 h, leaching temperature of 368 K and agitation rate of $400r{\cdot}min^{-1}$. The leaching rate of manganese, based on the shrinking core model, was found to be controlled by inner diffusion through the ash/inert layer composed of associated minerals. The activation energy of reductive leaching is $17.81kJ{\cdot}mol^{-1}$. To conclude the reaction mechanism, XRD analysis of leached ore residue indicates manganese compounds disappear; FTIR characterization of leached residue of black locust sawdust shows hemicellulose and cellulose disappear after the leaching process.

• Journal of the Korean Chemical Society
• /
• v.39 no.11
• /
• pp.842-847
• /
• 1995

The electrochemical reduction reactions of N '-aryl-N-alkyl-N-nitrosourea derivatives with a glassy carbon electrode were diffusion controlled and irreversible. The exchange kinetic constant ko values for reduction reaction of the N '-aryl-N-alkyl-N-nitrosoureas were at the range of $1.48{\times}10^{-6}{\sim}5.32{\times}10^{-7}\;cm/sec.$ The $k_0$ values for phenyl substituted on the aryl position were about 1.3∼2.8 times higher than that of other substituents. The same substituent for aryl groups on the both of N '-aryl-N-alkyl-N-nitrosourea and N '-aryl-N-(2-chloroethyl)-N-nitrosourea exhibited same value. The $E_p$ value was shifted to the negative direction as pH increased. The number of protons participated to the reduction was 4∼5, respectively. The substituent effect of aryl group on the reduction potential was not observed in this case.

• Journal of the Korean Chemical Society
• /
• v.27 no.3
• /
• pp.201-207
• /
• 1983

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

• Polymer(Korea)
• /
• v.37 no.3
• /
• pp.347-355
• /
• 2013

In this study, the porous cellulose hydrogel as a carrier to enhance the skin delivery of quercetin and its glycoside, rutin known as flavonoid antioxidants was prepared and its properties were investigated. The optimum cellulose hydrogel for quercetin and rutin was made by the reaction of 2 wt% cellulose with 12% ECH. In the release test of the hydrogel containing the flavonoids, the release of quercetin was diffusion-controlled at $10{\sim}500{\mu}M$, but rutin was released by the erosion of hydrogel system at $10{\sim}50{\mu}M$. Both the encapsulation efficiency and release amount of rutin in hydrogel were higher than quercetin. However, in skin permeation experiment using Franz diffusion cell, quercetin showed higher skin permeation capacity than rutin. The hydrogel containing flavonoids showed remarkable transdermal permeation than the control group. These results suggest that porous cellulose hydrogel is potential drug delivery system to enhance transdermal permeation of water-insoluble flavonoid antioxidants.

• Journal of the Korean Ceramic Society
• /
• v.42 no.4
• /
• pp.251-259
• /
• 2005

In order to characterize the influence of the reaction-site density on the cathodic polarization property of LSCF, we chose the porosity of LSCF as a main controlling variable, which is supposed to be closely related with active sites for the cathode reaction. To control the porosity of cathodes, we changed the mixing ratio of fine and coarse LSCF powders. The porosity and pore perimeter of cathodes were quantitatively analyzed by image analysis. The electrochemical half cell test for the cathodic polarization was performed via 3-probe AC-impedance spectroscopy. According to the investigation, the reduction of oxygen at LSCF cathode was mainly controlled by following two rate determining steps; i) surface diffusion and/or ionic conduction of ionized oxygen through bulk LSCF phase, ii) charge transfer of oxygen ion at cathode/electrolyte interface. Moreover, the overall cathode polarization was diminished as the cathode porosity increased due to the increase of the active reaction sites in cathode layer.

• Fire Science and Engineering
• /
• v.13 no.1
• /
• pp.37-47
• /
• 1999

The spreading fire of very small floating particles after they are ignited is fast and t therefore dangerous. The research on this area has been limited to experiments and global simulations which treat them as dusts or gaseous fuel with certain concentration well m mixed with air. This research attempted micro-scale analysis of ignition of those particles modeling them as liquid droplets. For the beginning, the in-line array of fuel droplets is modeled by two-dimensional, unsteady conservation equations for mass, momentum, energy and species transport in the gas phase and an unsteady energy equation in the liquid phase. They are solved numerically in a generalized non-orthogonal coordinate. The single step chemical reaction with reaction rate controlled by Arrhenius’ law is assumed to a assess chemical reaction numerically. The calculated results show the variation of temperature and the concentration profile with time during evaporation and ignition process. Surrounding oxygen starts to mix with evaporating fuel vapor from the droplet. When the ignition condition is met, the exothermic reactions of the premixed gas initiate a and burn intensely. The maximum temperature position gradually approaches the droplet surface and maximum temperature increases rapidly following the ignition. The fuel and oxygen concentration distributions have minimum points near the peak temperature position. Therefore the moment of ignition seems to have a premixed-flame aspect. After this very short transient period minimum points are observed in the oxygen and fuel d distributions and the diffusion flame is established. The distance between droplets is an important parameter. Starting from far-away apart, when the distance between droplets decreases, the ignition-delay time decreases meaning faster ignition. When they are close and after the ignition, the maximum temperature moves away from the center line of the in-line array. It means that the oxygen at the center line is consumed rapidly and further supply is blocked by the flame. The study helped the understanding of the ignition of d droplet array and opened the possibility of further research.

• Journal of the Korean Chemical Society
• /
• v.32 no.3
• /
• pp.233-242
• /
• 1988

The uranium(VI) complexes with new unsaturated macrocyclic ligands of cryptand types and the neodymium(III) complexes with cryptand 222 and DBC ligands have been investigated polarographically in dimethylsulfoxide solvent. The reduction states, electron numbers involved in the reduction process, effects of the added acid on the polarograms of complexes, and the mechanisms of the reduction electrode reactions have been examined. The stability constants and mole-ratio of new complexes were also obtained by polarographic method. The reaction of ligands was controlled by the diffusion in the reduction with four electrons at a step, whereas the redox reaction with six electrons at three steps in $UO_2\;^{2+}$ complexes with macrocyclic ligands and the redox reaction with one electron at a step in $Nd^{3+}$ complexes with cryptand 222 and DBC have been observed. The imine ligands formed stable complexes with uranium(VI) above pH 7.0, and the neodymium(III) complexes with cryptand 222 and DBC ligands were stable above pH 4.0.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.11 no.3
• /
• pp.127-131
• /
• 2001

The effect of grain shape on the grain growth behavior of oxide system was investigated as afunction of liquid content during liquid phase sintering. As a model system, the solid grains of $Al_{2}O_{3}$ and MgO were selected during liquid phase sintering, i.e. faceted shape of $Al_{2}O_{3}$ in $CaAl_{2}Si_{2}O_{8}$ liquid phase and spherical shape of MgO in $CaMgSiO_{4}$ liquid phase. The average grain size of MgO with spherical shape was decreased with increasing the liquid phase content, whereas that of $Al_{2}O_{3}$ with faceted shape was independent of liquid phase content. In the case of $Al_{2}O_{3}$ grains with faceted shape, which interfaces are expected to be atomically flat, are likely to grow by the interfacial reaction controled process. Whereas, in the case of MgO grains with spherical shape, which interface are expected to be atomically rough, are likely to grow by the diffusion controlled process.

• Korean Journal of Materials Research
• /
• v.17 no.7
• /
• pp.366-370
• /
• 2007

Silicon nitride ($Si_3N_4$) ceramics have been considered for various components of nuclear power plants such as the mechanical seal of a reactor coolant pump (RCP), the guide roller for a control rod drive mechanism (CRDM), and a seal support, etc. Corrosion behavior of $Si_3N_4$ ceramics in a high-temperature and high-pressure water must be elucidated before they can be considered as components for nuclear power plants. In this study, the corrosion behaviors of $Si_3N_4$ ceramics containing MgO and $Al_2O_3$ as sintering aids were investigated at a hydrothermal condition ($300^{\circ}C$, 9.0 MPa) in pure water and 35 ppm LiOH solution. The corrosion reactions were controlled by a diffusion of the reactive species and/or products through the corroded layer. The grain-boundary phase was preferentially corroded in pure water whereas the $Si_3N_4$ grain seemed to be corroded at a similar rate to the grain-boundary phase in LiOH solution. Flexural strengths of the $Si_3N_4$ ceramics were significantly degraded due to the corrosion reaction. Results of this study imply that a variation of the sintering aids and/or a control (e.g., crystallization) of the grain-boundary phase are necessary to increase the corrosion resistance of $Si_3N_4$ ceramics in a high-temperature water.