• 대한화학회지
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• 제33권2호
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• pp.168-176
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• 1989

화학 레이저 모델의 이론적 연구를 화학 반응속도론, gain 과정과 유도 방출과정을 고려하여 수행하였다. 우선 F+$H_2$비 연쇄반응 HF 화학 레이저를 진동준위가 v = 3 까지 pumping되는 것으로 생각하고 관련된 rate equation을 풀어서 출력을 산출하였다. 여기서 조화진동자를 가정한 계산과 비조화성 보정을 해준 계산결과의 비교로부터 그 차이가 거의 없음을 확인하였다. 또한 여러가지 온도와 초기농도를 택하여 산출되는 laser 축력의 변화를 검토하였다. 그리고 $H_2$+$F_2$ 연쇄반응 HF 화학 레이저에 관한 비교적 단순한 model simulation을 수행하였다. 이 계산 결과는 이미 보고된 상당히 복잡한 계산결과와 비교하여 만족할 정도이었다.

• 한국수소및신에너지학회논문집
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• 제22권3호
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• pp.363-371
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• 2011

In this paper, a three-dimensional hydrogen desorption model is developed to precisely study the hydrogen desorption kinetics and resultant heat and mass transport phenomena in metal hydride hydrogen storage vessels. The metal hydride hydrogen desorption model, i.e. governed by the conservation of mass, momentum, and thermal energy is first experimentally validated against the temperature evolution data measured on a cylindrical $LaNi_5$ metal hydride vessel. The equilibrium pressure used for hydrogen desorption simulations is derived as a function of H/M atomic ratio and temperature based on the experimental data in the literature. The numerical simulation results agree well with experimental data and the 3D desorption model successfully captures key experimental trends during hydrogen desorption process. Both the simulation and experiment display an initial sharp decrease in the temperature mainly caused by relatively slow heat supply rate from the vessel external wall. On the other hand, the effect of heat supply becomes influential at the latter stages, leading to smooth increase in the vessel temperature in both simulation and experiment. This numerical study provides the fundamental understanding of detailed heat and mass transfer phenomena during hydrogen desorption process and further indicates that efficient design of storage vessel and heating system is critical to achieve fast hydrogen discharging performance.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.833-838
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• 2014

The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to $C_7{H_7}^+$ (benzylium and tropylium). There are four different paths to $C_7{H_7}^+$, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to $C_7{H_7}^+$ is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

• ALGAE
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• 제30권1호
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• pp.35-47
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• 2015

The marine sand-dwelling dinoflagellate Polykrikos lebourae possesses obvious gold-brown pigmented plastids as well as taeniocyst-nematocyst complex structures. Despite of the presence of the visible plastids, previous attempts to establish this species in culture all failed and thus the unavailability of cultures of this species has posed a major obstacle to further detailed exploration of ecophysiology of the dinoflagellate. Here, we isolated P. lebourae from sandy sediment of an intertidal flat on Korean western coast, successfully established it in culture, and have been maintaining the stock culture over the past 3 years. Using this stock culture, we explored phagotrophy and potential prey resources of P. lebourae, growth and grazing responses of P. lebourae to different prey organisms, the effect of prey concentration on growth and grazing rates and gross growth efficiency (GGE) of P. lebourae when fed three different prey organisms, and the growth kinetics of P. lebourae under different light regimes. P. lebourae captured prey cells using a tow filament and then phagocytized them through the posterior end. The dinoflagellate was capable of ingesting a broad range of prey species varying in size, but not all prey species tested in this study supported its sustained growth. GGE of P. lebourae was extremely high at low prey concentration and moderate or low at high prey concentrations, indicating that P. lebourae grows heterotrophically at high prey concentrations but its growth seems to be more dependent on a certain growth factor or photosynthesis of plastids derived from the prey. In the presence of prey in excess, P. lebourae grew well at moderate light intensity of $40{\mu}mol$ photons $m^{-2}s^{-1}$, but did not grow at dim and high (10 or $120{\mu}mol$ photons $m^{-2}s^{-1}$) light intensities. Our results suggest that the benthic dinoflagellate P. lebourae is an obligate mixotroph, requiring both prey and light for sustained growth and survival.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.333-333
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• 2011

We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

• Advanced Composite Materials
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• 제17권2호
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• pp.157-166
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• 2008

In this study, multiwalled carbon nanotubes (MWCNTs) were compounded with the poly($\varepsilon$-caprolactone) (PCL) matrix at the solution state using chloroform. For homogeneous dispersion of MWCNTs in polymer matrix, oxygen-containing groups were introduced on the surface of MWCNTs. The mechanical properties of the PCL/MWCNTs composites were effectively increased due to the incorporation of MWCNTs. The composites were characterized using scanning electron microscopy in order to obtain information on the dispersion of MWCNT in the polymeric matrix. In case of 1.2 wt% of MWCNTs in the matrix, strength and modulus of the composite increased by 12.1% and 164.3%, respectively. In addition, the dispersion of MWCNTs in the PCL matrix resulted in substantial decrease of the electrical resistivity of the composites as the MWCNTs loading was increased from 0 to 2.0 wt%. Furthermore, thermal stability of the PCL and PCL/MWCNTs-COOH composites were investigated using the data acquired from the thermogravimetric analysis. The detailed kinetics of the thermal degradation of the composites was investigated by analyzing their thermal behavior at different heating rates in a nitrogen atmosphere. Activation energy of thermal degradation was determined by using the equations proposed by Kissinger and Flynn-Wall-Ozawa. The apparent activation energy of PCL/MWCNTs-COOH composite was considerably higher than that of neat PCL.

• 한국추진공학회지
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• 제20권2호
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• pp.46-55
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• 2016

Differential Scanning Calorimetry(DSC) 실험 데이터를 이용하여 고에너지 물질의 반응속도식을 추출해내는 이론적 방법을 제안하고 알루미늄 고함유 화약(RDX/HTPB/Al)에 대한 반응속도식 추출을 수행하였다. DSC 실험 결과는 Friedman 등전환법으로 분석되었다. 질량분율에 따른 활성화에너지와 빈도인자를 추출해 내어 반응속도식을 완성하였다. 추출된 반응속도식은 고에너지 물질의 화학반응과정을 몇 단계의 주요단계로 가정하는 형태가 아닌 전체 화학반응 과정을 나타내는 형태를 갖는다. 이는 기존의 ODTX 실험을 통해 추출되는 화학반응속도식 형태에 비해 이론적 측면과 정확성 측면에서 상당한 장점을 갖는다. 추출된 반응속도식의 검증을 위해 화학반응률 그리고 생성물 질량분율에 대해 DSC 실험과 동일한 조건하에서 전산모사를 수행하였으며 실험값과 잘 일치함을 확인하였다. 또한 완속가열 전산모사를 수행하였으며 실험결과와 비교하여 DSC 반응속도식의 전산모사에의 적용가능성을 확인하였다.

• 한국광물학회지
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• 제21권3호
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• pp.227-237
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• 2008

최근 들어 비소오염에 대한 환경적 관심이 증대되면서, 세계적으로 비소에 대한 음용수 기준이 강화되고 있으며, 국내적으로도 비소로 오열된 지하수 덴 토양의 출현 빈도가 높아지면서 비소 오염과 그에 대한 처리 및 대책이 주요한 환경적 관심사로 대두되고 있다. 지중에서 비소의 거동은 주로 산화물들과 점토광물에 의하여 제어되는데, 특히 철(산)수산화물이 가장 효과적으로 비소를 제어하는 것으로 알려져 있다. 이에 본 연구에서는 다양한 철(산)수산화물들 중 2-line ferrihydrite가 비소의 거동에 어떠한 영향을 미치는가를 파악하기 위하여 수행되어졌다. 다양한 비소 화학종들 중 자연 상에서 발현 빈도수가 가장 큰 3가 비소(아비산염)와 5가 비소(비산염)가 2-line ferrihydritc와 어떠한 흡착 특성을 갖는지 비교하여 연구하였다. 비소의 흡착제로 실험실에서 제조되어 이용된 2-line ferrihydrite는 $10\sim200nm$의 작은 나노 크기, $247m^{2}/g$의 비교적 큰 비표면적, 다른 철(산)수산화물보다 높은 8.2의 영전하 pH 등을 갖는 것으로 나타났는데, 이러한 2-line ferrihydrite의 대표적인 물리화학적인 특성들은 비소의 흡착제로서 매우 적합한 것으로 조사되었다. 평형흡착 실험결과, 3가 비소가 5가 비소보다 월등히 높은 흡착력을 보였으며, 3가 비소는 pH 7.0, 5가 비소는 pH 2.0에서 가장 놀은 흡착력을 보이는 것으로 나타났다. 3가 비소는 pH 12.2를 제외하고는 pH에 따른 흡착량이 크게 차이를 보이지 않은 반면, 5가 비소는 pH가 증가함에 따라 흡착량이 현격하게 갈소하는 것으로 나타났다. pH에 따른 비소의 흡착특성을 보다 더 자세하게 초찰한 견과, 3가 비소는 pH 8.0까지는 흡착량이 증가하다가 pH 9.2 이상에서는 흡착량이 급격하게 같소하는 것으포 나타났다. 5가 비소의 경우에는 pH가 증가할 수록 비교적 일정하게 흡착량이 갉소하는 것을 알 수 있었다. 이렇게 비소 화학종에 따라서 상이한 흡착특성을 보이는 이유는 pH에 따른 각 비소 화학종의 화학져 존재 형태(chemical speciation)와 2-line ferrihydrite의 표면전하의 변화 등이 복합적으로 작용하기 때문인 것으로 사료된다. 각 비소 화학종과 2-line ferrihyite와의 흡착특성을 반응속도론적 관점에서 고찰한 결과, 대부분의 비소종들이 2시간 이내에 흡착이 거의 완료되는 것으로 나타났으며, 두 종류의 비소 화학종과 2-line ferrihydrite의 흡착 반응속도를 가장 잘 모사하는 반응속도 모댁은 power function과 elovich model인 것으로 조사되었다.

• 한국산림과학회지
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• 제56권1호
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• pp.26-50
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• 1982

본(本) 연구(硏究)에서는 효소(酵素) 알칼리 증해(蒸解)의 리그닌 용출거동(溶出挙動) 파악하기 위(爲)해 잣나무(Pinus koraiensis S. et Z.) 목분(木粉)을 공시(供試)하여 $110^{\circ}C$, $120^{\circ}C$, $130^{\circ}C$, $140^{\circ}C$, 및 $150^{\circ}C$의 5 수준(水準) 온도(溫度)로 60분간(分間) 1단(段) 등온(等溫) 효소(酵素) 알칼리 탈(脱)리그닌 처리(処理)를 행(行)한 후(後), 그 탈(脱)리그닌 반응속도(反応速度), 활성화(活性化)에너지 및 반응시간별(反応時間別) 알칼리와 효소(酵素)의 소비동향(消費動向)을 동역학적(動力學的) 방법(方法)으로 구명(究明)하였다. 그 결과(結果)를 보면 탈(脱)리그닌은 반응초기(反応初期)에 전(全)리그닌 함량(含量)의 2/5가량이 급속(急速)히 용출(溶出)되는 초기(初期) 산화반응(酸化反応)을 나타냈다. 탈(脱)리그닌 반응(反応)의 속도상교(速度常敎)(K)는 반응온도(反応溫度) $150^{\circ}C$의 경우, 소오다법(法)에 비(比)해 3배정도(倍程度) 더 컸다. 본 법(法)의 활성화(活性化)에너지 값은 크라프트나 소오다 펄프법화(法化)보다 1/3정도(程度) 낮은 수준(水準)이었다. 알칼리소비량은 효소(酵素)의 경우와 마찬가지로 반응초기(反応初期)에 총투입량(總投入量)의 1/2가량이 급속히 소모된 후, 완만한 소비협추세(消費趨勢)를 보였다. 탈(脱)리그닌 반응속도(反応速度)는 증해과정중 생성되는 유기산(有機酸) 때문에 pH가 감소됨에 따라 크게 영향을 받았다. 또한 증해용출(蒸解溶出)된 리그닌은 잘 침전(沈澱)되지 않을 만큼 저분자화(低分子化) 됨을 알수 있었다. 리그닌의 메톡실기(基)는 급속히 감소(減少)되는데 반(反)해, 페놀성(性) 하이드록실기(基), 카보닐기(基) 및 카복실기(基)는 증가(增加)추세를 보였다.

• 한국추진공학회:학술대회논문집
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• 한국추진공학회 2003년도 제20회 춘계학술대회 논문집
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• pp.91-93
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• 2003

A comprehensive numerical study is carried out to investigate for the understanding of the flow evolution and flame development in a supersonic combustor with normal injection of ncumally injecting hydrogen in airsupersonic flows. The formulation treats the complete conservation equations of mass, momentum, energy, and species concentration for a multi-component chemically reacting system. For the numerical simulation of supersonic combustion, multi-species Navier-Stokes equations and detailed chemistry of H2-Air is considered. It also accommodates a finite-rate chemical kinetics mechanism of hydrogen-air combustion GRI-Mech. 2.11[1], which consists of nine species and twenty-five reaction steps. Turbulence closure is achieved by means of a k-two-equation model (2). The governing equations are spatially discretized using a finite-volume approach, and temporally integrated by means of a second-order accurate implicit scheme (3-5).The supersonic combustor consists of a flat channel of 10 cm height and a fuel-injection slit of 0.1 cm width located at 10 cm downstream of the inlet. A cavity of 5 cm height and 20 cm width is installed at 15 cm downstream of the injection slit. A total of 936160 grids are used for the main-combustor flow passage, and 159161 grids for the cavity. The grids are clustered in the flow direction near the fuel injector and cavity, as well as in the vertical direction near the bottom wall. The no-slip and adiabatic conditions are assumed throughout the entire wall boundary. As a specific example, the inflow Mach number is assumed to be 3, and the temperature and pressure are 600 K and 0.1 MPa, respectively. Gaseous hydrogen at a temperature of 151.5 K is injected normal to the wall from a choked injector.A series of calculations were carried out by varying the fuel injection pressure from 0.5 to 1.5MPa. This amounts to changing the fuel mass flow rate or the overall equivalence ratio for different operating regimes. Figure 1 shows the instantaneous temperature fields in the supersonic combustor at four different conditions. The dark blue region represents the hot burned gases. At the fuel injection pressure of 0.5 MPa, the flame is stably anchored, but the flow field exhibits a high-amplitude oscillation. At the fuel injection pressure of 1.0 MPa, the Mach reflection occurs ahead of the injector. The interaction between the incoming air and the injection flow becomes much more complex, and the fuel/air mixing is strongly enhanced. The Mach reflection oscillates and results in a strong fluctuation in the combustor wall pressure. At the fuel injection pressure of 1.5MPa, the flow inside the combustor becomes nearly choked and the Mach reflection is displaced forward. The leading shock wave moves slowly toward the inlet, and eventually causes the combustor-upstart due to the thermal choking. The cavity appears to play a secondary role in driving the flow unsteadiness, in spite of its influence on the fuel/air mixing and flame evolution. Further investigation is necessary on this issue. The present study features detailed resolution of the flow and flame dynamics in the combustor, which was not typically available in most of the previous works. In particular, the oscillatory flow characteristics are captured at a scale sufficient to identify the underlying physical mechanisms. Much of the flow unsteadiness is not related to the cavity, but rather to the intrinsic unsteadiness in the flowfield, as also shown experimentally by Ben-Yakar et al. [6], The interactions between the unsteady flow and flame evolution may cause a large excursion of flow oscillation. The work appears to be the first of its kind in the numerical study of combustion oscillations in a supersonic combustor, although a similar phenomenon was previously reported experimentally. A more comprehensive discussion will be given in the final paper presented at the colloquium.