• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1988-1992
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• 2010

4-Amino-1,2,4-triazole copper complex (4-ATzCu) was synthesized, and its thermal behaviors, nonisothermal decomposition reaction kinetics were studied by DSC and TG-DTG techniques. The thermal decomposition reaction kinetic equation was obtained as: $d\alpha$ / dt =$10^{22.01}$ (1-$\alpha$)[-ln(1-$\alpha$)]$^{1/3}$ exp($-2.75\times10^4$ /T). The standard mole specific heat capacity of the complex was determined and the standard molar heat capacity is 305.66 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ at 298.15 K. The entropy of activation $({\Delta}S^{\neq})$, enthalpy of activation $({\Delta}H^{\neq})$, and Gibbs free energy of activation $({\Delta}G^{\neq})$ are calculated as 171.88 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ 225.81 $kJ{\cdot}mol^{-1}$ and 141.18 $kJ{\cdot}mol^{-1}$, and the adiabatic time-to-explosion of the complex was obtained as 389.20 s.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2267-2273
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• 2011

A novel energetic material, 1-amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene (APHDNE), was synthesized by the reaction of 1,1-diamino-2,2-dinitroethylene (FOX-7) and 2,4-dinitrophenylhydrazine in N-methyl pyrrolidone (NMP) at 110 $^{\circ}C$. The theoretical investigation on APHDNE was curried out by B3LYP/6-311+$G^*$ method. The IR frequencies analysis and NMR chemical shifts were performed and compared with the experimental results. The thermal behavior of APHDNE was studied by DSC and TG/DTG methods, and can be divided into two crystal phase transition processes and three exothermic decomposition processes. The enthalpy, apparent activation energy and pre-exponential factor of the first exothermic decomposition reaction were obtained as -525.3 kJ $mol^{-1}$, 276.85 kJ $mol^{-1}$ and $10^{26.22}s^{-1}$, respectively. The critical temperature of thermal explosion of APHDNE is 237.7 $^{\circ}C$. The specific heat capacity of APHDNE was determined with micro-DSC method and theoretical calculation method, and the molar heat capacity is 363.67 J $mol^{-1}K^{-1}$ at 298.15 K. The adiabatic time-to-explosion of APHDNE was also calculated to be a certain value between 253.2-309.4 s. APHDNE has higher thermal stability than FOX-7.

• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2259-2264
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• 2009

A new high-energy organic potassium salt, 2-(dinitromethylene)-1,3-diazepentane potassium salt K(DNDZ), was synthesized by reacting of 2-(dinitromethylene)-1,3-diazepentane (DNDZ) and potassium hydroxide. The thermal behavior and non-isothermal decomposition kinetics of K(DNDZ) were studied with DSC, TG/DTG methods. The kinetic equation is $\frac{d{\alpha}}{dT}$ = $\frac{10^{13.92}}{\beta}$3(1 - $\alpha$[-ln(1 - $\alpha$)]$^{\frac{2}{3}}$ exp(-1.52 ${\times}\;10^5$ / RT). The critical temperature of thermal explosion of K(DNDZ) is $208.63\;{^{\circ}C}$. The specific heat capacity of K(DNDZ) was determined with a micro-DSC method, and the molar heat capacity is 224.63 J $mol^{-1}\;K^{-1}$ at 298.15 K. Adiabatic time-to-explosion of K(DNDZ) obtained is 157.96 s.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2867-2872
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• 2010

Two new energetic organic alkali metal salts, 1,1-diamino-2,2-dinitroethylene rubidium salt [Rb(FOX-7)${\cdot}H_2O$] and 1,1-diamino-2,2-dinitroethylene cesium salt [Cs(FOX-7)${\cdot}H_2O$], were synthesized by reacting of 1,1-diamino-2,2-dinitroethylene (FOX-7) and rubidium chloride or cesium chloride in alkali methanol aqueous solution, respectively. The thermal behaviors of Rb(FOX-7)${\cdot}H_2O$ and Cs(FOX-7)${\cdot}H_2O$ were studied with DSC and TG methods. The critical temperatures of thermal explosion of the two compounds are 216.22 and $223.73^{\circ}C$, respectively. Specific heat capacities of the two compounds were determined with a micro-DSC method, and the molar heat capacities are 217.46 and $199.47\;J\;mol^{-1}\;K^{-1}$ at 298.15 K, respectively. The adiabatic times-to-explosion were also calculated to be a certain value of 5.81 - 6.36 s for Rb(FOX-7)${\cdot}H_2O$, and 9.92 - 10.54 s for Cs(FOX-7)${\cdot}H_2O$. After FOX-7 becoming alkali metal salts, thermal decomposition temperatures of the compounds heighten with the rise of element period, but thermal decomposition processes become intense.

• 대한기계학회논문집B
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• 제35권5호
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• pp.451-457
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• 2011

본 연구의 주 목적은 연료 수분 미소 정량 공급기를 장착한 층류 반응기(LFR)에서 수분함량 변화에 따른 석탄의 휘발분 점화 특성을 조사하는 것이다. 실제 발전소의 미분기 출구 분위기와 비슷한 수분량이 석탄량의 20, 30, 40%로 LFR에 석탄과 함께 공급했을 때 휘발분의 점화 위치와 시간을 실험적으로 관찰하였다. 석탄이 공급되는 층류 반응기 정 중앙의 수직방향으로 $70{\mu}m$ R-type 열전대를 이용하여 복사 열손실을 고려한 가스온도를 측정하였고, 휘발분 점화 위치는 CCD 카메라를 이용해 촬영한 15~20개의 이미지를 디지털 이미지 프로세싱을 통해 얻은 평균 값으로 결정하였다. 그 결과 수분량이 증가할수록 가스 온도는 감소하였고, 점화 위치는 2.92, 3.36, 3.96, 4.65mm로 지수적으로 증가하였다. 이러한 실험결과는 이론적으로 adiabatic thermal explosion에서의 점화 지연 시간과 같은 경향을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2352-2358
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• 2012

A high-nitrogen energetic salt, 1-amino-1-hydrazino-2,2-dinitroethylene guanidine salt [G(AHDNE)], was synthesized by reacting of 1-amino-1-hydrazino-2,2-dinitroethylene (AHDNE) and guanidine hydrochloride in sodium hydroxide aqueous solution. The theoretical investigation on G(AHDNE) was carried out by B3LYP/$6-311+G^*$ method. The thermal behaviors of G(AHDNE) were studied with DSC and TG-DTG methods, and the result presents an intense exothermic decomposition process. The enthalpy, apparent activation energy and pre-exponential constant of the process are $-1060J\;g^{-1}$, $148.7kJ\;mol^{-1}$ and $10^{15.90}s^{-1}$, respectively. The critical temperature of thermal explosion of G(AHDNE) is $152.63^{\circ}C$. The specific heat capacity of G(AHDNE) was studied with micro-DSC method and theoretical calculation method, and the molar heat capacity is $314.69J\;mol^{-1}K^{-1}$ at 298.15 K. Adiabatic time-to-explosion of G(AHDNE) was calculated to be a certain value between 60-72 s. The detonation velocity and detonation pressure were also estimated. G(AHDNE) presents good performances.