• Macromolecular Research
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• 제13권5호
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• pp.427-434
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• 2005

To improve the performance and reduce raw material costs, blocked isocyanates were prepared with mixture of blocking agents in many industries. Three blocked isocyanates (adducts) namely $\varepsilon$-caprolactam/benzotriazole-blocked 4,4'-diphenylmethane diisocyanate (MDI), toluene-2,4-diisocyanate (TDI) and 4,4'-dicyclohexyl-methane diisocyanate ($H_{12}$MDI) were synthesized. Six reference adducts were also prepared by blocking MDI, TDI, and $H_{12}$MDI with $\varepsilon$-caprolactam ($\varepsilon$-CL) or benzotriazole. The reactions were carried out in acetone medium and dibutyltin dilaurate (DBTDL) was used as a catalyst. The progress of the blocking reaction was monitored by IR spectroscopy. De-blocking temperatures (dissociation temperatures) of these adducts were studied using DSC and TGA and the results were correlated. As expected, the thermal analysis data showed that de-blocking temperature of blocked aromatic isocyanates was lower than that of the blocked aliphatic isocyanates. The low de-blocking temperature of blocked aromatic isocyanate could be due to electron withdrawing benzene ring present in the blocked isocyanates. It was also found that benzotriazole-blocked adducts de-blocked at higher temperature compared with $\varepsilon$-CL-blocked adducts.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2004년도 하계학술대회 논문집 Vol.5 No.1
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• pp.215-219
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• 2004

This paper is investigated about the effect of carrier gas and humidity for generating hydrogen gas. In the experimental result of generating hydrogen gas by non-thermal plasma reactor, the rate of generating hydrogen gas is different with what kind of carrier gas is. We used two types of carrier gas, such as $N_2$ and He. $N_2$ as carrier gas is more efficient to generate hydrogen gas than He because $N_2$ is reacted with $O_2$, which is made from water dissociation. In comparison with no humidity and humidity 45[%], the generation of hydrogen gas is decreased with increasing the humidity. That is the result that the energy for water dissociation is reduced on water surface because a part of plasma energy is absorbed at the small particle produced from humidifier.

• Mass Spectrometry Letters
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• 제15권1호
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• pp.54-61
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• 2024

An improved voltage modulation method (VMM) was used to control the heat release and adsorption properties of the adsorbent. In this work, the voltage and flux modulation methods were considered under unified experimental conditions of dissociative surface ionization (SI) of polyatomic organic molecules, the criteria were found when under VMM conditions the current relaxation of SI carries information about the kinetic properties of thermal desorption of ionizable dissociation particles arriving on the surface of polyatomic molecules. Conditions were found under which the relaxation of the ionic current in the flux modulation method is determined by the kinetics of the heterogeneous dissociation reaction of the original polyatomic molecules. The values of the thermal desorption rate constant K⁺ and the activation energy E⁺ obtained with VMM for desorption of (CH₃)₂NCH⁺₂ ions with m/z 58 by adsorption of imipramine and amitriptyline molecules agree well with each other and with the results for the desorption of the same ions by adsorption of other molecules. This confirms one of the basic conditions for the equilibrium process SI - the a degree (β coefficient) of the same particles SI on the same emitter surface is the same and does not depend on the way these particles are formed on the emitter surface.

• 대한전기학회:학술대회논문집
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• 대한전기학회 2011년도 제42회 하계학술대회
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• pp.1584-1585
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• 2011

분자의 전리(ionization)작용과 이온의 해리(dissociation)작용에 의한 유전체 내 방전해석을 위해서 전자, 양이온, 음이온의 생성과 소멸, 전자부착, 재결합 과정을 포함한 전하연속방정식, 전계에 의한 푸아송 방정식, 유전체 온도에 관한 열확산 방정식을 결합하여 해석하였다. 전계 방출 조건과 열전자 방출 조건이 경계조건으로 부여되었고 에너지 최소화 정류조건을 따르는 유한요소법(finite element method)을 이용하여 해석하였다. 비교적 작은 값을 가지는 확산성을 무시하고 대류성에 역점을 두어 발생하는 수치적 불안정은 인공확산항(artificial diffusion technique)을 도입하여 안정화하였다. 본 논문에서는 IEC standard 60897의 표준규격에 따른 2차원 축대칭 침-구 전극에 적용하여 제안된 다중물리해석기법의 타당성을 입증하였다.

• 한국가스학회지
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• 제19권3호
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• pp.54-59
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• 2015

가스하이드레이트(GH: Gas Hydrate)는 전 세계적으로 약 10조 톤에 이르는 엄청난 양이 대부분 해양의 대륙사면에 부존되어 있으나(동토 지역 : 2 %, 해양 대륙사면 98 %), 현재까지 가스하이드레이트 저류층으로부터 상업화할 수 있을 만큼 가스를 회수하는 기술이 개발되어 있지 않은 실정이다. 일반적으로 회수하는 방법은 감압법, 열자극법, 억제재 주입법 및 치환법 등으로 크게 나누어 볼 수 있으며, 본 연구에서는 가스하이드레이트 포화율과 감압률에 따라서 가스하이드레이트 해리시간 및 가스생산이 어떻게 달라지는 지, 그에 대한 특성을 분석하고자 하였다. 연구분석 결과 감압률과 해리시간의 상관 관계식을 도출($Y=0.0004X^2-0.499X+176.86$)할 수 있었고, 또한 감압률이 클수록 메탄생산량이 좋다는 것을 알 수 있었지만(감압률 40% 대비 50%에서 메탄가스생산량이 46.2% 향상), 감압률이 60%에서는 오히려 생산량이 줄어드는데, 이는 가스하이드레이트 재형성에 기인한 것으로 판단된다.

• 한국자원공학회지
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• 제55권6호
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• pp.670-687
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• 2018

본 논문에서는 미래 에너지로서 가스 하이드레이트를 이해하기 위해, 가스 하이드레이트의 구조, 물리/화학적 특성, 생성 기원과 세계 분포, 매장량과 생산기법, 하이드레이트의 지구환경적 영향에 대해 논의하였다. 하이드레이트의 구조에 대한 명확한 이해는 자연계에 매장된 하이드레이트의 특성 분석, 분포와 매장량 산출에 필수적일 것으로 판단된다. 안정적인 에너지 회수를 위해 고려해야 할 하이드레이트의 물리/화학적 특성으로는 하이드레이트의 상평형, 해리 엔탈피, 열전도도, 비열, 열확산도, 유체투과율 등이 있다. 하이드레이트의 물리/화학적 특성을 고려하여 개발된 생산기법으로는 감압법, 열자극법, 억제제 주입법, 맞교환기법이 있으며, 감압법이 현재까지 해상 및 육상 하이드레이트에 대해 모두 시험생산에 적용된 유일한 기법이다. 또한, 하이드레이트의 해리에 따른 온실가스 배출에 의한 지구환경적 영향의 가능성에 대해서도 고찰하였다.

• 한국안전학회지
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• 제16권2호
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• pp.75-79
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• 2001

For handling and storage of reactive chemicals, the hazard evaluations have been extremely important. In the chemical industry, the most concerns are focused on the thermal harzards such as runaway reactions and thermal decompositions, which are mostly governed by thermodynamics and reaction kinetics or these reactive chemical in the system. This study no investigated the thermal decomposition characteristics of nitrophenylhydrazine isomers by using differential scanning calorimeter(DSC) and accelerating rate calorimeter(ARC). Experimental results showed that exothermic onset-temperatures in nitrophenylhydrazine(NPH) isomers were about 160-$210^{\circ}C$ by DSC and 100-$150^{\circ}C$ by ARC. The decomposition temperature acquired by ARC was about 50-$60^{\circ}C$ lower than that by DSC. Reaction heats were about 40-100cal/g by DSC and 330-750ca1/g by ARC. While ortho isomer of NPH show two distinct exothermic peaks, para isomer shows a single peak in DSC curves. The first exothermic peak for 2-NPH is mainly due to intramolecular dehydration forming 1-hydroxybenzotriazole(HOBT) and the second exothermic peak is mainly due to the decomposition of HOBT formed in the first step of decomposition. The exothermin peak in the DSC curve for 4-NPH is mainly due to dissociation of hydrazino and nitro groups.

• Macromolecular Research
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• 제16권6호
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• pp.561-566
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• 2008

NR composites with different curing systems were aged thermally at 60, 70, 80, and $90^{\circ}C$ for 2-185 days in a convection oven, and the changes in the crosslink density were investigated as a function of the accelerated thermal aging. The overall crosslink densities increased with increasing aging time irrespective of the aging temperatures and curing systems. The changes in crosslink density were enhanced by increasing the aging temperature. The degree of the increased crosslink density was in the following order: "the conventional cure system > the semi-EV system > the EV system". For short term thermal aging, the change in crosslink density with the aging time was complicated, particularly for low temperature aging. The activation energies of the change in crosslink density with thermal aging using the conventional and semi-EV cure systems increased and then remained relatively constant with increasing aging time, whereas that of the specimen with an EV cure system tended to increase linearly. The experimental results were explained by the dissociation of the existing polysulfidic linkages and the formation of new cross links through the crosslinking-related chemicals remaining in the sample.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.564-570
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• 2012

s-Tetrazine is the essential candidate of many energetic compounds due to its high nitrogen content, enthalpy of formation and thermal stability. The present study explores the design of s-tetrazine derivatives in which different $-NO_2$, $-NH_2$ and $-N_3$ substituted azoles are attached to the tetrazine ring via C-N linkage. The density functional theory (DFT) is used to predict the geometries, heats of formation (HOFs) and other energetic properties. The predicted results show that azide group plays a very important role in increasing HOF values of the s-tetrazine derivatives. The densities for designed molecules were predicted by using the crystal packing calculations. The introduction of $-NO_2$ group improves the density as compared to $-N_3$, and $-NH_2$ groups and hence the detonation performance. Bond dissociation energy analysis and insensitivity correlations revealed that amino derivatives are better candidates considering insensitivity and stability.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1043-1049
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• 2014

Density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) theoretical level were performed for two novel explosives (compounds B and C) based on the guanidine-fused bicyclic skeleton $C_4N_6H_8$ (A). The heats of formation (HOFs) were calculated via isodesmic reaction. The detonation properties were evaluated by using the Kamlet-Jacobs equations. The bond dissociation energies (BDEs) for the thermolysis initiation bond were also analyzed to investigate the thermal stability. The results show that the compounds have high positive HOF values (B, 1064.68 $kJ{\cdot}mol^{-1}$; C, 724.02 $kJ{\cdot}mol^{-1}$), high detonation properties (${\rho}$, D and P values of 2.04 $g{\cdot}cm^{-3}$ and 2.21 $g{\cdot}cm^{-3}$, 9.98 $km{\cdot}s^{-1}$ and 10.99 $km{\cdot}s^{-1}$, 46.44 GPa and 59.91 Gpa, respectively) and meet the basic stability requirement. Additionally, feasible synthetic routes of the these high energy density compounds (HEDCs) were also proposed via retrosynthetic analysis.