• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2454-2458
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• 2007

Exploring the basic concepts for the design of CO2-philic molecules is important due to the possibility for “green” chemistry in supercritical CO2 as substitute solvent systems. The Lewis acid-base interactions and C?H…O weak hydrogen bonding were suggested as two key factors for the solubility of CO2-philic molecules. We have performed high level quantum mechanical calculations for the van der Waals complexes of CO2 with trimethylphosphate and trimethylphosphine oxide, which have long been used for metal extractants in supercritical CO2 fluid. Structures and energies were calculated using the MP2/6-31+G(d) and recently developed multilevel methods. These studies indicate that the Lewis acid-base interactions have larger impact on the stability of structure than the C?H…O weak hydrogen bonding. The weak hydrogen bonds in trimethylphosphine oxide have an important role to the large supercritical CO2 solubility when a metal is bound to the oxygen atom of the P=O group. Trimethylphosphate has many Lewis acid-base interaction sites so that it can be dissolved into supercritical CO2 easily even when it has metal ion on the oxygen atom of the P=O group, which is indispensable for a good extractant.

• 센서학회지
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• 제25권6호
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• pp.423-430
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• 2016

This study used a single metal oxide semiconductor (MOS) sensor to classify the major odorous gases hydrogen sulfide ($H_2S$), ammonia ($NH_3$) and toluene ($C_6H_5CH_3$). In order to classify these odorous substances, the voltage on the MOS sensor heater was gradually reduced in 0.5 V steps 5.0 V to examine the changes to the response by the cooling effect on the sensor as the voltage decreased. The hydrogen sulfide gas showed the highest sensitivity compared to odorless air under approximately 2.5 V and the ammonia and toluene gases showed the highest sensitivity under approximately 5.0 V. In other words, the hydrogen sulfide gas reacted better in the low temperature range of the MOS sensor, and the ammonia and toluene gases reacted better in the high-temperature range. In order to analyze the response characteristics of the MOS sensor by temperature in a pattern, a two-dimensional (2D) x-y pattern analysis was introduced to clearly classify the hydrogen sulfide, ammonia, and toluene gases. The hydrogen sulfide gas was identified by a straight line with a slope of 1.73, whereas the ammonia gas had a slope of 0.05 and the toluene gas had a slope of 0.52. Therefore, the 2D x-y pattern analysis is suggested as a new way to classify these odorous substances.

• Korean Journal of Chemical Engineering
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• 제35권11호
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• pp.2321-2326
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• 2018

We evaluated the optimal conditions for fluidization of nickel oxide (NiO) and its reduction into high-purity Ni during hydrogen reduction in a laboratory-scale fluidized bed reactor. A comparative study was performed through structural shape analysis using scanning electron microscopy (SEM); variance in pressure drop, minimum fluidization velocity, terminal velocity, reduction rate, and mass loss were assessed at temperatures ranging from 400 to $600^{\circ}C$ and at 20, 40, and 60 min in reaction time. We estimated the sample weight with most active fluidization to be 200 g based on the bed diameter of the fluidized bed reactor and height of the stocked material. The optimal conditions for NiO hydrogen reduction were found to be height of sample H to the internal fluidized bed reactor diameter D was H/D=1, reaction temperature of $550^{\circ}C$, reaction time of 60 min, superficial gas velocity of 0.011 m/s, and pressure drop of 77 Pa during fluidization. We determined the best operating conditions for the NiO hydrogen reduction process based on these findings.

• 한국수소및신에너지학회논문집
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• 제22권5호
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• pp.616-624
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• 2011

Hydrogen storage and release of Fe/Zr/Mo mixed oxide mediums were investigated by hydrogen reduction and water splitting oxidation($Fe_3O_4+4H_2{\rightleftharpoons}3Fe+4H_2O$). As the results of TPR/O, Mo was an additive to enhance the reactivity of water splitting oxidation as well as the stability of the medium. On the other hand, it seemed that $ZrO_2$ additive provided the passway for the diffusion of gaseous chemicals on the medium in repeated redox cycles. Among the Fe/Zr/Mo mediums, a FeZrMo-7 medium (Fe/Zr/Mo=80/13/7mol%) exhibited the best performance with good durability during five repeated redox cycles. The amount of hydrogen evolved on the medium was maintained at ca. 10.7mmol-$H_2$/g-medium corresponding to the hydrogen storage amount of ca. 2.2wt%.

• 한국재료학회지
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• 제18권11호
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• pp.597-603
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• 2008

Oxide effects experiments on massive hydriding reactions of Zr alloy with hydrogen gas were carried out at $400^{\circ}C$ under 1 atm in a $H_2$ environment with a thermo-gravimetric apparatus (TGA). Experimental results for oxide effects on massive hydriding kinetics show that incubation time is not proportional to oxide thickness. The results also show that the massive hydriding kinetics of pre-filmed Zr alloys follows linear kinetic law and that the hydriding rates are similar to that of oxide-free Zr alloys once massive hydriding is initiated. Unlikely microstructure of the oxide during incubation time, physical defects such as micro-cracks and pores were observed in the oxide after incubation time. Therefore, it seems that the massive hydriding of Zr alloys can be ascribed to short circuit paths and mechanical or physical defects, such as micro-cracks and pores in the oxide, rather than to hydrogen diffusion through the oxide resulting from the increase of oxygen vacancies in the hypo-stoichiometric oxide.

• 한국수소및신에너지학회논문집
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• 제17권1호
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• pp.82-89
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• 2006

The redox behaviors of anode-supported flat tube for solid oxide fuel cell has been studied. The mass change of the extruded NiO/YSZ anode flat tube during redox cycling was examined by thermogravimetric analysis(TGA). The result of TGA was shown a rapidly mass change in the range of $455\;-\;670^{\circ}C$ and the reoxidation of the NiO/YSZ anode was almost completed at $750^{\circ}C$. The starting temperature of reoxidation and the maximum temperature of oxidation rate decreased with increasing the reoxidation cycle, which is attributed to the increased porosity caused by volume change. Bending strengths of the NiO/YSZ anode after redox cycling were 96 - 80 MPa and the bending strength decreased slightly with increasing the redox cycle. On the other hand, the bending strength of the NiO/YSZ anode with electrolyte showed 130 MPa after first redox cycling but decreased rapidly with increasing the redox cycle. From the results of the bending test and the microstructure observation, we conclude that the crack initiation of the electrolyte-coated NiO/YSZ anode was induced easily at interface of electrolyte/anode tube and propagated cross the electrolyte.

• 한국수소및신에너지학회논문집
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• 제22권5호
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• pp.649-655
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• 2011

Methane direct cracking can be utilized to produce $CO_x$ and $NO_x$-free hydrogen for PEM fuel cells, oil refineries, ammonia and methanol production. We present the results of a systematic study of methane direct cracking using a mixed conducting oxide, Y-doped $BaZrO_3$ ($BaZr_{0.85}Y_{0.15}O_3$), membrane. In this paper, dense $BaZr_{0.85}Y_{0.15}O_3$ membrane with disk shape was successfully sintered at $1400^{\circ}C$ with a relative density of more 93% via addition of 1 wt% ZnO. The ($BaZr_{0.85}Y_{0.15}O_3$) membrane is covered with Pd as catalyst for methane decomposition with an DC magnetron sputtering method. Reaction temperature was $800^{\circ}C$ and high purity methane as reactant was employed to membrane side with 1.5 bar pressure. The $H_2$ produced by the reaction was transported through mixed conducting oxide membrane to the outer side. In addition, it was observed that the carbon, by-product, after methane direct cracking was deposited on the Pd/ZnO-$BaZr_{0.85}Y_{0.15}O_3$ membrane. The produced carbon has a shape of sphere and nanosheet, and a particle size of 80 to 100 nm.

• 한국재료학회지
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• 제19권6호
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• pp.325-329
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• 2009

Titanium dioxide thin films were fabricated as hydrogen sensors and its sensing properties were tested. The titanium was deposited on a $SiO_2$/Si substrate by the DC magnetron sputtering method and was oxidized at an optimized temperature of $850^{\circ}C$ in air. The titanium film originally had smooth surface morphology, but the film agglomerated to nano-size grains when the temperature reached oxidation temperature where it formed titanium oxide with a rutile structure. The oxide thin film formed by grains of tens of nanometers size also showed many short cracks and voids between the grains. The response to 1% hydrogen gas was ${\sim}2{\times}10^6$ at the optimum sensing temperature of $200^{\circ}C$, and ${\sim}10^3$ at room temperature. This extremely high sensitivity of the thin film to hydrogen was due partly to the porous structure of the nano-sized sensing particles. Other sensor properties were also examined.

• 한국수소및신에너지학회논문집
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• 제30권4호
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• pp.303-311
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• 2019

Reversible solid oxide fuel cell (RSOFC) has become a prospective device for energy storage and hydrogen production. Many studies have been conducted around the world focusing on system efficiency improvement and realization. The system should have not only high efficiency but also a certain level of simplicity for stable operation. External waste steam utilization was proved to remarkably increase the efficiency at solid oxide electrolysis system. In this study, RSOFC system coupled with waste steam was proposed and optimized in term of simplicity and efficiency. Ejector for fuel recirculation is selected due to its simple design and high stability. Three system configurations using ejector for fuel recirculation were investigated for performance of design condition. In parametric study, the system efficiencies at different current density were analyzed. The system configurations were simulated using validated lumped model in EBSILON(R) program. The system components, balance of plants, were designed to work in both electrolysis and fuel cell modes, and their off-design characteristics were taken into account. The base case calculation shows that, the system with suction pump results in slightly lower efficiency but stack can be operated more stable with same inlet pressure of fuel and air electrode.

• 전력전자학회:학술대회논문집
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• 전력전자학회 2008년도 하계학술대회 논문집
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• pp.646-648
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• 2008

The multi-films of a metallic film and a transparent conducting oxide (TCO, indium-tin oxide, ITO) film were formed on the stainless steel 316 and 304 plates by a sputtering method and an E-beam method and then the external metallic region of the stainless steel bipolar plates was converted into the metal nitride films through an annealing process. The multi-film formed on the stainless steel bipolar plates showed the XRD patterns of the typical indium-tin oxide, the metallic phase and the metal substrate and the external nitride film. The XRD pattern of the thin film on the bipolar plates modified showed two metal nitride phases of CrN and $Cr_2N$ compound. Surface microstructural morphology of the multi-film deposited bipolar plates was observed by AFM and FE-SEM. The electrical resistivity of the stainless steel bipolar plates modified was evaluated.