• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.26-31
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• 2023

For durability improvement of polymer electrolyte membrane fuel cell (PEMFC) polymer membrane, accelerated durability evaluation methods that can evaluate durability in a short time have been researched and developed. However, the lifespan of fuel cells for large commercial vehicles such as trucks and buses is more than three times that of passenger cars, and the chemical accelerated stress test (AST) time is also longer, reaching 1,500 hours or more. Therefore, in this study, as a method to evaluate the chemical durability of a membrane within a short time, it was examined whether the durability could be predicted by the pristine membrane characteristics. Hydrogen crossover current density (HCCD) and short resistance (SR) were estimated as initial characteristics, and AST time was predicted through the Fenton experiment, which was possible as an out-of-cell experiment for 3 hours. As the HCCD and fluoride ion emission concentration increased, the AST time tended to be linearly shortened, but there was a deviation (R² ≒0.65). When the SR decreased, the AST time showed a linear increase, and the accuracy was high (R² =0.93), so the AST time could be predicted with the initial SR of the membrane.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.189-195
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• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.341-347
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• 2023

In PEMFC, PtCo/C alloy catalysts are widely used because of good performance and durability. However, few studies have been reported on the durability of carbon supports of PtCo/C evaluated at high voltages (1.0~1.5 V). In this study, the durability of PtCo/C catalysts and Pt/C catalysts were compared after applying the accelerated degradation protocol of catalyst support. After repeating the 1.0↔1.5V voltage change cycles, the mass activity, electrochemical surface area (ECSA), electric double layer capacitance (DLC), Pt dissolution and the particle growth were analyzed. After 2,000 cycles of voltage change, the current density per catalyst mass at 0.9V decreased by more than 1.5 times compared to the Pt/C catalyst. This result was because the degradation rate of the carbon support of the PtCo/C catalyst was higher than that of the Pt/C catalyst. The Pt/C catalyst showed more than 1.5 times higher ECSA reduction than the PtCo/C catalyst, but the corrosion of the carbon support of the Pt/C catalyst was small, resulting in a small decrease in I-V performance. In order to improve the high voltage durability of the PtCo/C catalyst, it was shown that improving the durability of the carbon support is essential.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.362-367
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• 2023

Recently, research and development of proton exchange membrane fuel cells (PEMFC) membranes are progressing in the direction of thinning to reduce prices and improve performance. Demand for hydrogen-powered vehicles for commercial vehicles is also increasing, and their durability should be five times greater than those for passenger vehicles. Despite the thinning of the membranes, the durability of the membranes must be increased five times, so the improvement of the durability of the membranes has become more important. Since the acceleration durability evaluation time also needs to be shortened, the protocol using oxygen instead of air in the existing protocol was applied to a 10 ㎛ thin membrane to evaluate durability. The accelerated durability test (Open circuit voltage holding) was terminated at 720 hours. If the air-based department of energy (DOE) protocol was used, a lifespan of 450,000 km of driving hours would be expected, with a durability of about 1,500 hours. During the chemical durability evaluation, the active area of the electrode decreased by 51%, suggesting that catalyst degradation had an effect on membrane durability. Reducing the catalyst degradation rate is expected to increase membrane durability.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.356-361
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• 2023

In order to improve the durability of the proton exchange membrane fuel cell (PEMFC), it is important to accurately evaluate the durability of the polymer membrane in a short time. The test conditions for chemically accelerated durability evaluation of membranes are high voltage, high temperature, low humidity, and high gas pressure. It can be said that the protocol is developed by changing these conditions. However, the relative influence of each test condition on the degradation of the membrane has not been studied. In chemical accelerated degradation experiment of the membrane, the influence of 4 factors (conditions) was examined through the factor experiment method. The degree of degradation of the membrane after accelerated degradation was determined by measuring the hydrogen permeability and effluent fluoride ion concentration, and it was possible to determine the degradation order of the polymer membrane under 8 conditions by the difference in fluoride ion concentration. It was shown that the influence of the membrane degradation factor was in the order of voltage > temperature > oxygen pressure > humidity. It was confirmed that the degradation of the electrode catalyst had an effect on the chemical degradation of the membrane.

• Korean Chemical Engineering Research
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• v.61 no.4
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• pp.517-522
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• 2023

A chemical/mechanical durability test of polymer membrane evaluation method is used in which air and hydrogen are supplied to the proton exchange membrane fuel cell (PEMFC) and wet/dry is repeated in the open circuit voltage (OCV) state. In this protocol, when wet/dry is repeated, voltage increase/decrease is repeated, resulting in electrode degradation. When the membrane durability is excellent, the number of voltage changes increases and the evaluation is terminated due to electrode degradation, which may cause a problem that the original purpose of membrane durability evaluation cannot be performed. In this study, the same protocol as the department of energy (DOE) was used, but oxygen was used instead of air as the cathode gas, and the wet/dry time and flow rate were also increased to increase the chemical/mechanical degradation rate of the membrane, thereby shortening the durability evaluation time of the membrane to improve these problems. The durability test of the Nafion 211 membrane electrode assembly (MEA) was completed after 2,300 cycles by increasing the acceleration by 2.6 times using oxygen instead of air. This protocol also accelerated degradation of the membrane and accelerated degradation of the electrode catalyst, which also had the advantage of simultaneously evaluating the durability of the membrane and the electrode.

• Korean Chemical Engineering Research
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• v.62 no.1
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• pp.1-6
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• 2024

As the demand for hydrogen electric vehicles for commercial vehicles increases, the durability of PEMFCs must increase more than five times that of passenger cars, so research and development to improve durability is urgent. When the PEMFC membrane electrode assembly (MEA) undergoes chemical degradation, the MEA thickness decreases and pinholes occur. In this study, changes in the performance and durability of the MEA were measured while increasing the clamping pressure of the unit cell after open circuit voltage (OCV) holding, an accelerated chemical degradation experiment. As the clamping pressure increased, the resistance of the polymer membrane and the membrane/electrode contact resistance decreased, improving the I-V performance and reducing the hydrogen permeability. As the hydrogen permeability decreased, the OCV increased. When the pinhole area was removed and the MEA clamping pressure was increased, the hydrogen permeability decreased sharply, confirming that the local degradation has a large effect on the performance and durability of the entire cell. When the pinhole was removed and re-clamping and OCV holding was evaluated, it was confirmed that the durability improved according to the decrease in membrane resistance and hydrogen permeability.

• Korean Chemical Engineering Research
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• v.62 no.1
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• pp.7-12
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• 2024

The durability of the catalyst support has a significant effect on the durability of proton exchange membrane fuel cells (PEMFC). The accelerated durability evaluation of the catalyst support is performed at a high voltage (1.0 to 1.5 V), and the catalyst and ionomer binder in the catalyst layer are also deteriorated, hindering the evaluation of the durability of the support. The existing protocol (DOE protocol) was improved to find conditions in which the support, which is a durability evaluation target, deteriorates further. A protocol (MDOE) was developed in which the relative humidity was lowered by 35% and the number of voltage changes was reduced. After repeating the 1.0 ↔ 1.5 V voltage change cycle, the catalyst mass activitiy (MA), electrochemical active area (ECSA), electrical double layer capacity (DLC), Pt dissolution and particle growth were analyzed. Reaching 40% reduction in mass activity, the MDOE protocol took only 500 cycles, reducing the number of voltage changes compared to the DOE method and increasing the degradation of the carbon support by 50% compared to the DOE protocol.

• Economic and Environmental Geology
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• v.38 no.4 s.173
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• pp.435-450
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• 2005

The purpose of the study is to analyze the hydrogeochemical characteristics by multivariate statistical method, to interpret the hydrogeochemical processes for the new variables calculated from principal components analysis (PCA), and to infer the groundwater flow and circulation mechanism by applying the geostatistical methods for each element and principal component. Chloride and nitrate are the most influencing components for groundwater quality, and the contents of $NO_3$ increased by the input of agricultural activities show the largest variation. The results of PCA, a multivariate statistical method, show that the first three principal components explain $73.9\%$ of the total variance. PC1 indicates the increase of dissolved ions, PC2 is related with the dissolution of carbonate minerals and nitrate contamination, and PC3 shows the effect of cation exchange process and silicate mineral dissolution. From the results of experimental semivariogram, the components of groundwater are divided into two groups: one group includes electrical conductivity (EC), Cl, Na, and $NO_3$, and the other includes $HCO_3,\;SiO_2,$ Ca, and Sr. The results for spatial distribution of groundwater components showed that EC, Cl, and Na increased with approaching the coastal line and nitrate has close relationship with the presence of agricultural land. These components are also correlated with the topographic features reflecting the groundwater recharge effect. The kriging analysis by using principal components shows that PC 1 has the different spatial distribution of Cl, Na, and EC, possibly due to the influence of pH, Ca, Sr, and $HCO_3$ for PC1. It was considered that the linear anomaly zone of PC2 in western area was caused by the dissolution of carbonate mineral. Consequently, the application of multivariate and geostatistical methods for groundwater in the study area is very useful for determining the quantitative analysis of water quality data and the characteristics of spatial distribution.

• Korean Journal of Heritage: History & Science
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• v.56 no.3
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• pp.138-156
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• 2023

Some of the metal cultural heritage that make up a considerable proportion of Korea's cultural heritage have been installed and displayed outdoors due to their own functions, roles, and scale. Therefore, more diverse and complex damages can occur outdoors than they are in a stable environment. Therefore, it is necessary to combine accurate diagnosis and systematic survey methods in order to utilize basic data obtained from research results as data for the long-term and continuous conservation management as well as to do the research to diagnose the conservation status of outdoor cultural heritage. The clepsydra(hereinafter referred to as Jagyeongnu) of Changgyeonggung Palace, the National Treasure has been installed and displayed outdoors since it was manufactured. Though regular conservation and maintenance of the Jagyeongnu have been carried out, damage still occurred. Therefore, the scientific research on Jagyeongnu to diagnose the state of conservation was conducted prior to the full-scale conservation treatment. First, the state of conservation was investigated with an examination of basic data, macroscopic inspections and past records of repair history according to the purpose of the research. More detailed examinations were also conducted through the 3D scan, surface pattern investigation, and color difference analysis, and the analysis on materials and contaminants were conducted through P-XRF, FT-IR, and Py-GC/MS. The scientific research reveals that squalane and silicone oil have been applied in the past for conservation treatment and directly exposed to outdoor environmental factors, which caused damage to Jagyeongnu and contaminants such as dust adhered thickly to its surface, accelerating severe damage. A greater incidence of damage was found around the part with relatively high exposure effect, which corresponded with the tendency identified by grouping color difference data. As a result of integrating various research methodologies to diagnose the state of conservation and secure basic data, the causes and types of damage were identified. Furthermore, the process of obtaining digital data to be utilized in various ways, and the color difference analysis presenting visible damage as scientific data and identifying the tendency of damage patterns were confirmed to have been effective.