• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.239-239
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• 2003

탄소재료의 산화반응을 설명한 대부분의 논문은 TGA(Thermo Gravimetric Analysis)를 이용한 연구이다. TGA 장치는 가열이 필요한 물질의 반응연구에 다양하게 이용되고 있는데, 온도에 대한 무게 변화를 간편하게 알 수 있다는 장점과 함께 보편적으로 편리한 Arrhenius형태의 속도식으로 해석된다. 많은 연구자들은 TGA를 이용하여 다양한 탄소재료에 대한 반응속도상수를 구하였으며, 반응기체, 반응온도 및 원료물질에 따라 다른 속도를 나타내는 실험결과를 표준화된 속도식으로 표현하고자 하는 노력이 있었다. 그러나 이런 대부분의 연구는 coal 등과 같은 탄소재료의 연소특성을 이용하려는 에너지 변환 연구가 주를 이루어 왔으며, 탄소섬유의 산화반응에 대한 표준화 식으로 해석한 보고는 거의 없는 실정이다. 이 연구에서는 내부구조가 현격하게 차이나는 다른 두 종류의 피치계 탄소섬유를 TGA를 이용하여 등온 산화반응 시켰다. 반응기체의 종류와 반응온도를 변화시켜 산화반응조건에 따른 중량변화를 관찰하였고, 여러 산화조건에서 얻어진 산화속도를 Kasaoka 등에 의해 제안된 표준화식을 이용하여 산화반응의 평균 속도상수 K와 전환율이 0.5일 때의 속도상수 $k_{f=0.5}$ 결과를 비교하여 산화 반응속도를 정량적으로 해석하고자 하였다.다.

• Electrical & Electronic Materials
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• v.4 no.4
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• pp.344-353
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• 1991

무정형 SiC 박막을 수평형 CVD반응기로부터 SiH$_{4}$ 및 H$_{2}$를 반응기체로 하여 실리콘 웨이퍼위에 증착시켜 제조하였다. 박막 성장 속도는 상압에서 650.deg.C와 850.deg.C범위에서 측정되었다. 반응기체의 유량은 1000sccm으로 고정하였으며 SiH$_{4}$와 CH$_{4}$의 유량을 변화시켰다. 증착 반응속도식으로 표면 반응이 율속단계인 Eley-Rideal 모델과 SiH$_{4}$와 CH$_{4}$의 종도에 m차로 비례하는 두가지 속도식을 가정하였다. 증착시간에 따른 SiC 박막두께의 측정으로부터 얻은 증착 반응 속도로부터 회귀 분석법에 의하여 두가지 반응속도식의 반응속도 상수를 구하였다. 얻어진 반응속도식에 의해서 계산된 값과 실험치를 비교한 결과 0.15차의 반응속도식이 Eley-Rideal반응기구보다 약산 더 잘 맞음을 알 수 있으나 두 모델 다 약간씩 실험결과와 차이가 나고 있다. 이것은 본 실험의 증착 조건의 율속단계가 확산 단계와 표면 반응 단계의 전이영역 즉 본 실험의 증착조건에서 확산속도와 표면 반응속도가 비슷하기 때문으로 생각된다. 또한 Eley-Rideal 반응기구에서 부터 얻어진 SiH$_{4}$ 및 CH$_{4}$의 흡착평형상수 $K_{s}$ 와 $K_{c}$ 값을 비교하면 1000K이하에서는 $K_{s}$ 가 $K_{c}$ 보다 큰 값을 가지는데 이것은 Gibbs 자유에너지 최소화 방법에서 구한 결과와 일치하였다.

• Journal of the Korean Society of Propulsion Engineers
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• v.19 no.1
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• pp.33-41
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• 2015

The kinetic analysis of energetic materials using Differential Scanning Calorimetry (DSC) is proposed. Friedman Isoconversional method is applied to DSC experiment data and AKTS software is used for analysis. The proposed kinetic scheme has considerable advantage over the standard method based on One-Dimenaionl Time to Explosion (ODTX). Reaction rate and product mass fraction simulation are conducted to validate extracted kinetic scheme. Also a slow cook-off simulation is implemented on $B/KNO_3$ for validating the applicability of the extracted kinetics scheme to a practical thermal experiment.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.358-364
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• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

• Journal of the Korean Society of Propulsion Engineers
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• v.20 no.2
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• pp.46-55
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• 2016

The kinetic analysis of a heavily aluminized cyclotrimethylene-trinitramine(RDX) is conducted using differential scanning calorimetry(DSC), and the Friedman isoconversional method is applied to the DSC experimental data. The pre-exponential factor and activation energy are extracted as a function of the product mass fraction. The extracted kinetic scheme does not assume multiple chemical steps to describe the complex response of energetic materials; instead, a set of multiple Arrhenius factors is constructed based on the local progress of the exothermic reaction. The resulting reaction kinetic scheme is applied to two thermal decomposition tests for validating the reactive flow response of a heavily aluminized RDX. The results support applicability of the present model to practical thermal explosion systems.

• Clean Technology
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• v.19 no.1
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• pp.51-58
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• 2013

In this study, kinetics data was obtained for steam reforming reaction of ethane over the nickel catalyst. The variables of steam reforming reaction were reaction temperature, partial pressure of ethane, and mole ratio of steam and ethane. Parameters for the power rate law kinetic model and the Langmuir-Hinshelwood model were obtained from the kinetic data. Also, sizing of steam reforming reactor was performed by using PRO/II simulator. For the steam reforming reaction of ethane, Langmuir-Hinshelwood model determining the reaction rate by the surface reaction was better suited than a simple power rate law kinetic model. On water-gas-shift reaction, power rate law kinetic model was well fitted to the kinetic data. Reactor size can be calculated for production of hydrogen through PRO/II simulation.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2017.05a
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• pp.547-553
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• 2017

Thermal analysis of three energetic materials used in pyroelectric device was performed using Differential Scanning Calorimetry (DSC). The theoretical method for extracting the reaction rate equation of energetic materials using DSC experimental data is proposed and the reaction rate extraction is performed. The results of the DSC were analyzed by the conversion method such as Friedman. Activation energy and frequency factor according to mass fraction were extracted to complete the reaction rate equation. The extracted reaction rate equation has a form that represents the entire chemical reaction process, not the assumption that the chemical reaction process of the high energy material is a main step in several stages. It has considerable advantages in terms of theoretical and accuracy as compared with the chemical reaction rate form extracted through conventional thermal analysis experiments. Using the derived reaction rate equation, we predicted the performance change of three energetic materials operating on actual storage condition over 20 years.

• The Journal of Engineering Research
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• v.3 no.1
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• pp.223-233
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• 1998

The kinetic and mechanism of the hydrothermal reaction between lime and quartz used solid state reaction equations have been investigated. Hydrothermal reaction on the starting materials was carried out in an autoclave that quartz mixed with calcium hydroxide in CaO/$SiO_2$ ratio of 0.8-1.0 for 0.5-8 hour at saturated steam pressure of $180-200^{\circ}C$. The rate of reaction was given from the ratio of uncombined lime and quartz content to the total lime and quartz content. The rate of reaction was obtained the results by the Jander's equation $[1-(1-\alpha)^{1/3}]^N=Kt$. The reaction of lime is controlled mainly by the dissolution such as N=1, and the reaction of quartz is controlled mostly by the diffusion such as $N\risingdotseq2$. The rate of hydrothermal reaction in the calcium silicate hydrates system is suggested to be determined generally by the mass transfer through the product laver formed around the reactant particles. The rate equation for whole hydrothermal reaction is shown that it is converted into the rate determining step by the diffusion from the boundary reaction such as approximately $N=1-2$.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.77.2-77.2
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• 2010

일산화탄소를 수소로 변환하는 수성가스전환반응(WGSR)은 수소 생산, 연료개질 시스템뿐만 아니라 암모니아 제조, 제철소 제련과정등 일선 산업현장에서 널리 활용되고 있다. 상용공정에서의 WGS반응은 두 단계의 반응기(HTS/LTS)에서 각각 Fe/Cr, Cu/Zn기반 촉매를 사용하여 이루어진다. 하지만 이러한 촉매들은 공기중 자연발화성이 있고 사용전 환원과정이 필요하다. 또한 최근에 많은 연구가 진행되고 있는 귀금속 담지 촉매는 기존 촉매의 단점을 극복하고 활성이 높은 장점이 있다. 이에 본 연구에서 제시한 페로브스카이트 촉매는 상용 촉매, 귀금속 담지촉매 시스템과의 비교를 위하여 제작된 촉매를 사용한 반응시스템과 기존 상용촉매를 사용한 반응시스템을 비교하여 개발 촉매의 성능 수준을 검토하였다. 이러한 결과 페로브스카이트 구조 촉매는 상용촉매의 공정상의 단점과 귀금속 담지촉매의 가격적인 측면에서의 단점을 동시에 극복한 촉매로서 성능 및 메탄화반응 억제 측면에서 우수성을 보유하고 있다는 것을 증명하였다. 이러한 페로브스카이트 구조 촉매의 반응특성을 규명하기 위해 문헌조사해본 결과 기존 수성가스전환반응에서 쓰이는 촉매들의 반응매카니즘은 대표적으로 formate와 redox 반응 두가지가 있었다. 페로스브스카이트 구조 촉매는 그 구조와 귀금속 함량, 활성 등 성능측면에서 귀금속 촉매와 상당히 유사한 측면이 있기 때문에 귀금속 담지 촉매의 반응속도식을 기본으로 하여 실험결과와 일치시켜 페로브스카이트구조 촉매에 맞는 반응속도식을 제시하고 이를 통한 반응파라미터 값을 도출하였다.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.111-118
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• 1991

The kinetic of the gas phase reactions of ozone(0.5 torr) with sulfur dioxide was studied. The SO2 reaction was conducted in the 7∼22 torr range at 90∼155$^{\circ}$C. The reaction rate was faster than the reaction rate of O$_3$ in the presence of CO$_2$ alone. The reaction of O$_3$ with SO$_2$ follows the rate law: -d(O$_3)/dt=k_0(SO_2)(M)(O_3)+2k _1(SO_2)(O_3$). The first term of this rate law arises from a third order molecular reaction predominating in the lower temperature range and gave a rate constant k$_0$ = (9.35 $\pm$ 8.6) ${\times}$ 10$^9$e$^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$). The second term of the above rate law derived from a second order thermal decomposition reaction which was the major part of the reaction and gave a rate constant k$_0 =(9.35{\pm}8.6){\times}10^9e^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$). The overall reaction proceeds with kinetics of complex order composed mainly of second order and third order components.