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Anomalous Luminescence and Emission Quenching Behaviors of Tris(2,2$^\prime$-bipyridine)Ruthenium(Ⅱ) in Poly(methacrylic acid) Solutions$^1$

  • Park, Joon-Woo;Paik, Young-Hee
    • Bulletin of the Korean Chemical Society
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    • v.7 no.2
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    • pp.137-142
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    • 1986
  • The luminescence spectra of $Ru(bpy)_3^{2+}$ in poly(methacrylic acid) (PMA) solutions varied sensitively with pH. At pH < 5.5, the emission intensity increased with pH up to 4 times, while it decreased with pH beyond the pH. The enhanced emission intensity was accompanied by blue-shift of the emission maxima as much as 15 nm. The enhancement of emission intensity was attributed to the restricted rotational mobility of ligand of the cation bound to densely coiled PMA molecules at pH < 5.5. The sharp decrease in emission intensity with increasing pH near pH 5.6 was accounted for conformational transition of the polymer to more extended structure, which was also revealed in viscosity measurement. The enhancement of emission intensity became higher as NaCl concentration of the solution increased. The binding constant of $Ru(bpy)_3^{2+}$ with two carboxylate groups of PMA was calculated as $2{\times}10^5\;M^{-1}$ in 0.1 M NaCl at pH 5.2. The pH dependence of luminescence quenching rate of $Ru(bpy)_3^{2+}$ by $Cu^{++}$ also showed maximum near pH 5, and the rate was more than $10^3$ times higher than that in water, whereas the maximum enhancement of quenching rate (about 20 times) in poly(acrylic acid) (PAA) solution occurred at pH 4.5. On the other hand, the pH dependence for neutral water soluble nitrobenzene (NB) exhibited opposite trend to that of $Cu^{++}$. The quenching constant vs pH curve for $MV^{++}$ was composite of those for $Cu^{++}$ and NB. The anomalous high quenching rate for $Cu^{++}$ in PMA solution at pH < 5.5 was attributed to the binding of $Ru(bpy)_3^{2+}$ and $Cu^{++}$ to the same region of PMA, when it conforms densely coiled structure in the pH range. The observation of mininium quenching rate for NB near pH 5.5 indicated that the $Ru(bpy)_3^{2+}$ bound to the densely coiled PMA is not accessible by NB, which is in bulk water phase. The composite nature of the pH dependence of quenching rate for $MV^{++}$ in PMA solution was attributed to the smaller binding affinity of the cation to PMA, compared to that of $Cu^{++}$. The sharp, cooperative conformational transition with pH observed in PMA was not revealed in PAA. But, the pH dependence of quenching rates in this polymer reflected increased charge density and, thus, binding of cations to the polymer, and expansion of the polymer chain with pH.

Pseudo-Static Behaviors of U-shaped PSC Girder with Wide Flanges (확폭플랜지를 갖는 U형 프리스트레스 거더의 유사정적거동)

  • Rhee, In-Kyu;Lee, Joo-Beom;Kim, Lee-Hyeon;Park, Joo-Nam;Kwak, Jong-Won
    • Proceedings of the KSR Conference
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    • 2008.11b
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    • pp.993-999
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    • 2008
  • A girder height limitation is the critical parameter for rapid construction of bridge deck and construction space limitation especially in urban area such as high population area and high density habitats. A standard post-tensioned I-shaped concrete girder usually demands relatively higher girder height in order to retain sufficient moment arm between compression force and tensile force. To elaborate this issue, a small U-shaped section with wide flanges can be used as a possible replacement of I-shaped standard girder. This prestressed concrete box girder allows more flexible girder height adjustment rather than standard I-shaped post-tensioned girder plus additional torsion resistance benefits of closed section. A 30m-long, 1.7m-high and 3.63m-wide actual small prestressed concrete box girder is designed and a laboratory test for its static behaviors by applying 6,200kN amount of load in the form of 4-point bending test was performed. The load-deflection curve and crack patterns at different loading stage are recorded. In addition, to extracting the dynamic characteristics such as natural frequency and damping ratio of this girder, several excitation tests with artificial mechanical exciter with un-symmetric mass are carried out using operational frequency sweep-up. Nonlinear finite element analysis of this 4 point bending test under monotonic static load is investigated and discussed with aids of concrete damaged plasticity formulation using ABAQUS program.

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Effect of Lithium Contents and Applied Pressure on Discharge Characteristics of Single Cell with Lithium Anode for Thermal Batteries (리튬 함량 및 단위 셀 압력이 열전지용 리튬 음극의 방전 성능에 미치는 영향)

  • Im, Chae-Nam;Ahn, Tae-Young;Yu, Hye-Ryeon;Ha, Sang Hyeon;Yeo, Jae Seong;Cho, Jang-Hyeon;Yoon, Hyun-Ki
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.32 no.2
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    • pp.165-173
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    • 2019
  • Lithium anodes (13, 15, 17, and 20 wt% Li) were fabricated by mixing molten lithium and iron powder, which was used as a binder to hold the molten lithium, at about $500^{\circ}C$ (discharge temp.). In this study, the effect of applied pressure and lithium content on the discharge properties of a thermal battery's single cell was investigated. A single cell using a Li anode with a lithium content of less than 15 wt% presented reliable performance without any abrupt voltage drop resulting from molten lithium leakage under an applied pressure of less than $6kgf/cm^2$. Furthermore, it was confirmed that even when the solid electrolyte is thinner, the Li anode of the single cell normally discharges well without a deterioration in performance. The Li anode of the single cell presented a significantly improved open-circuit voltage of 2.06 V, compared to that of a Li-Si anode (1.93 V). The cut-off voltage and specific capacity were 1.83 V and $1,380As\;g^{-1}$ (Li anode), and 1.72 V and $1,364As\;g^{-1}$ (Li-Si anode). Additionally, the Li anode exhibited a stable and flat discharge curve until 1.83 V because of the absence of phase change phenomena of Li metal and a subsequent rapid voltage drop below 1.83 V due to the complete depletion of Li at the end state of discharge. On the other hand, the voltage of the Li-Si anode cell decreased in steps, $1.93V{\rightarrow}1.72V(Li_{13}Si_4{\rightarrow}Li_7Si_3){\rightarrow}1.65V(Li_7Si_3{\rightarrow}Li_{12}Si_7)$, according to the Li-Si phase changes during the discharge reaction. The energy density of the Li anode cell was $807.1Wh\;l^{-1}$, which was about 50% higher than that of the Li-Si cell ($522.2Wh\;l^{-1}$).

Machine Learning Model to Predict Osteoporotic Spine with Hounsfield Units on Lumbar Computed Tomography

  • Nam, Kyoung Hyup;Seo, Il;Kim, Dong Hwan;Lee, Jae Il;Choi, Byung Kwan;Han, In Ho
    • Journal of Korean Neurosurgical Society
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    • v.62 no.4
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    • pp.442-449
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    • 2019
  • Objective : Bone mineral density (BMD) is an important consideration during fusion surgery. Although dual X-ray absorptiometry is considered as the gold standard for assessing BMD, quantitative computed tomography (QCT) provides more accurate data in spine osteoporosis. However, QCT has the disadvantage of additional radiation hazard and cost. The present study was to demonstrate the utility of artificial intelligence and machine learning algorithm for assessing osteoporosis using Hounsfield units (HU) of preoperative lumbar CT coupling with data of QCT. Methods : We reviewed 70 patients undergoing both QCT and conventional lumbar CT for spine surgery. The T-scores of 198 lumbar vertebra was assessed in QCT and the HU of vertebral body at the same level were measured in conventional CT by the picture archiving and communication system (PACS) system. A multiple regression algorithm was applied to predict the T-score using three independent variables (age, sex, and HU of vertebral body on conventional CT) coupling with T-score of QCT. Next, a logistic regression algorithm was applied to predict osteoporotic or non-osteoporotic vertebra. The Tensor flow and Python were used as the machine learning tools. The Tensor flow user interface developed in our institute was used for easy code generation. Results : The predictive model with multiple regression algorithm estimated similar T-scores with data of QCT. HU demonstrates the similar results as QCT without the discordance in only one non-osteoporotic vertebra that indicated osteoporosis. From the training set, the predictive model classified the lumbar vertebra into two groups (osteoporotic vs. non-osteoporotic spine) with 88.0% accuracy. In a test set of 40 vertebrae, classification accuracy was 92.5% when the learning rate was 0.0001 (precision, 0.939; recall, 0.969; F1 score, 0.954; area under the curve, 0.900). Conclusion : This study is a simple machine learning model applicable in the spine research field. The machine learning model can predict the T-score and osteoporotic vertebrae solely by measuring the HU of conventional CT, and this would help spine surgeons not to under-estimate the osteoporotic spine preoperatively. If applied to a bigger data set, we believe the predictive accuracy of our model will further increase. We propose that machine learning is an important modality of the medical research field.

A Simple Method for the Estimation of Hyperelastic Material Properties by Indentation Tests (압입시험을 통하여 초탄성 재료 물성치를 평가하는 단순한 방법)

  • Song, Jae-Uk;Kim, Min-Seok;Jeong, Gu-Hun;Kim, Hyun-Gyu
    • Journal of the Computational Structural Engineering Institute of Korea
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    • v.32 no.5
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    • pp.273-278
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    • 2019
  • In this study, a new simple method for the estimation of hyperelastic material properties by indentation tests is proposed. Among hyperelastic material models, the Yeoh model with three material properties ($C_{10}$, $C_{20}$, $C_{30}$) is adopted to describe the strain energy density in terms of strain invariants. Finite element simulations of the spherical indentation of hyperelastic materials of the Yeoh model with different material properties are performed to establish a database of indentation force-displacement curves. The indentation force-displacement curves are fitted by cubic polynomials, which are approximated as a product of third-order polynomials of ($C_{10}$, $C_{20}$, $C_{30}$). A regression analysis is conducted to determine the coefficients of the equations for the indentation force-displacement curve approximations. A regression equation is used to estimate the hyperelastic material properties. The present method is verified by comparing the estimated material properties with true values.

Analysis of the Influence of Road·Traffic Conditions and Weather on the Take-over of a Conditional Autonomous Vehicle (도로·교통 조건 및 기상 상황이 부분 자율주행자동차의 제어권전환에 미치는 영향 분석)

  • Park, Sungho;Yun, YongWon;Ko, Hangeom;Jeong, Harim;Yun, Ilsoo
    • The Journal of The Korea Institute of Intelligent Transport Systems
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    • v.19 no.6
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    • pp.235-249
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    • 2020
  • The Ministry of Land, Infrastructure and Transport established safety standards for Level 3 autonomous vehicles for the first time in the world in December 2019, and specified the safety standards for conditional autonomous driving systems. Accordingly, it is necessary to analyze the influence of various driving environments on take-over. In this study, using a driving simulator, we investigated how traffic conditions and weather conditions affect take-over time and stabilization time. The experimental procedure was conducted in the order of preliminary training, practice driving, and test driving, and the test driving was conducted by dividing into a traffic density and geometry experiment and a weather environment experiment. As a result of the experiment, it was analyzed that the traffic volume and weather environment did not affect the take-over time and take-over stabilization time, and only the curve radius affects take-over stabilization time.

A study on estimation of lowflow indices in ungauged basin using multiple regression (다중회귀분석을 이용한 미계측 유역의 갈수지수 산정에 관한 연구)

  • Lim, Ga Kyun;Jeung, Se Jin;Kim, Byung Sik;Chae, Soo Kwon
    • Journal of Korea Water Resources Association
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    • v.53 no.12
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    • pp.1193-1201
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    • 2020
  • This study aims to develop a regression model that estimates a low-flow index that can be applied to ungauged basins. A total of 30 midsized basins in South Korea use long-term runoff data provided by the National Integrated Water Management System (NIWMS) to calculate average low-flow, average minimum streamflow, and low-flow index duration and frequency. This information is used in the correlation analysis with 18 basin factors and 3 climate change factors to identify the basin area, average basin altitude, average basin slope, water system density, runoff curve number, annual evapotranspiration, and annual precipitation in the low-flow index regression model. This study evaluates the model's accuracy by using the root-mean-square error (RMSE) and the mean absolute error (MAE) for 10 ungauged, verified basins and compares them with the previous model's low-flow calculations to determine the effectiveness of the newly developed model. Comparative analysis indicates that the new regression model produces average low-flow, attributed to the consideration of varied basin and hydrologic factors during the new model's development.

Multi-Layered Sintered Porous Transport Layers in Alkaline Water Electrolysis (다층 소결메쉬 확산체를 이용한 알칼라인 수전해 셀)

  • YEOM, SANG HO;YUN, YOUNG HWA;CHOI, SEUNGWOOK;KWON, JIHEE;LEE, SECHAN;LEE, JAE HUN;LEE, CHANGSOO;KIM, MINJOONG;KIM, SANG-KYUNG;UM, SUKKEE;KIM, CHANG-HEE;CHO, WON CHUL;CHO, HYUN-SEOK
    • Journal of Hydrogen and New Energy
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    • v.32 no.6
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    • pp.442-454
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    • 2021
  • The porous transport layer (PTL) is essential to effectively remove oxygen and hydrogen gas from the electrode surface at high current density operation conditions. In this study, the effect of PTL with different characteristics such as pore size, pore gradient, interfacial coating was investigated by multi-layered sintered mesh. A water electrolysis single cell of active area of the 34.56 cm2 was constructed, and IV performance and impedance analysis were conducted in the range of 0 to 2.0 A/cm2. It was confirmed that the multi-layered sintered mesh PTL, which have an average pore size of 25 to 57 ㎛ and a larger pore gradient, removed bubbles effectively and thus seemed to improve IV performance. Also, it was confirmed that the catalytic metals such as Ni, NiMo coating on the PTL reduced activation overpotential, but increased mass transport overpotential.

Analysis of calcium fluoride single crystal grown by the czochralski method (초크랄스키 방법으로 성장한 CaF2 단결정 분석)

  • Lee, Ha-Lin;Na, Jun-Hyuck;Park, Mi-Seon;Jang, Yeon-Suk;Jung, Hea-Kyun;Kim, Doo-Gun;Lee, Won-Jae
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.32 no.6
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    • pp.219-224
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    • 2022
  • CaF2 single crystal has a large band gap (12 eV), and it is used for optical windows, prisms, and lenses due to its excellent transmittance in a wide wavelength range and low refractive index. Moreover, it is expected to be one of the materials for ultraviolet transmissive laser optical components. CaF2 belongs to the fluoride compounds and has a face-centered cubic (FCC) structure with three sub-lattices. The representative method for CaF2 single crystal growth is Czochralski, which method has the advantages of high production efficiency and the ability to make large crystals. In this study, X-ray diffraction (XRD), X-ray rocking curves (XRC) measurement, and chemical etching were performed to analyze the crystallinity and defect density of the CaF2 single crystals, grown by the Czochralski method. Fourier-transform infrared spectroscopy (FT-IR) and UV-VIS-NIR spectroscopy systems were used to investigate the optical properties of the CaF2 crystal. The provability of various applications, including UV application, was systematically investigated with various analysis results.

Effects of Carbon Dioxide Concentration on Functional Response of Aphidius colemani Viereck (Hymenoptera: Braconidae) on the Green Peach Aphid (복숭아혹진딧물에 대한 콜레마니진디벌 기능반응에 미치는 이산화탄소 농도 영향)

  • Jeong Joon Ahn;Jung-Eun Kim;Chun Hwan Kim
    • Korean journal of applied entomology
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    • v.62 no.3
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    • pp.155-160
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    • 2023
  • In this study, we investigated the functional response of aphid parasitoid, Aphidius colemani Viereck (Hymenoptera: Braconidae), on the green peach aphid, Myzus persicae (Sulzer) (Hemiptera: Aphididae). Three carbon dioxide concentrations (400, 600, and 1000ppm) and seven host densities (2, 4, 8, 16, 32, 64, and 128) were used during a 24-h period. A type III functional response for A. colemani was fit separately for each CO2 concentration. The estimated handling time (Th) under elevated CO2 (600 ppm and 1000 ppm, 0.015 and 0.014 day) was shorter than that under ambient CO2 (400 ppm, 0.017 day). The proportion of aphids that were parasitized showed the similar characteristic curve under three CO2 concentrations. The highest parasitized rates for A. colemani were 0.57, 0.61, and 0.70 at 16, 32, and 32 aphid density under 400, 600, and 1000ppm, respectively. Although handling time of A. colemani was influenced by elevated CO2 concentrations, the attach rate was not changed much.