Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Synthesis and Characterization of Guanidine Dinitramide Crystal

구아니딘 디나이트라아마이드 결정의 합성 및 특성 분석

  • Kim, Wooram (Department of Applied Environmental Science, Kyun Hee University) ;
  • Kwon, Younja (Department of Applied Environmental Science, Kyun Hee University) ;
  • Jo, Youngmin (Department of Applied Environmental Science, Kyun Hee University) ;
  • Park, Youngchul (Agency for Defense Development 4th R&D Institute 1 Department)
  • 김우람 (경희대학교 환경응용과학과) ;
  • 권윤자 (경희대학교 환경응용과학과) ;
  • 조영민 (경희대학교 환경응용과학과) ;
  • 박영철 (국방과학연구소 4 기술연구본부)
  • Received : 2015.10.16
  • Accepted : 2015.11.16
  • Published : 2015.12.10
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Abstract

An environmentally favorable solid oxidizer, guanidine dinitramide ($H_2C(NH_2)NH_2N(NO_2)_2$), with high purity and synthesis yield was prepared using guanidine carbonate ($NH_2C(=NH)NH_2{\cdot}1/2H_2CO_3$). Two different crystalline forms (${\alpha}$-form and ${\beta}$-form) were obtained depending on the solvent used and synthesis process. Despite of the same chemical composition, Raman-IR and TGA-DSC revealed that different structures existed between them. In particular, the thermal analysis showed the exothermic temperature of ${\alpha}$-form at $155.7^{\circ}C$ while $191.6^{\circ}C$ for ${\beta}$-form. The caloric value of ${\alpha}$-form was 536.4 J/g which was 2.5 times larger than that of ${\beta}$-form, 1310 J/g. In addition, ${\alpha}$-form was steeply decomposed with one-step variation, but ${\beta}$-form followed a two-step thermal decomposition pattern.

친환경 고체산화제 GDN (guanidine dinitramide, $NH_2C(NH_2)NH_2N(NO_2)_2$)을 ADN (ammonium dinitramide, $NH_4N(NO_2)_2$)과 구아니딘 카보네이트(guanidine carbonate, $NH_2C(=NH)NH_2{\cdot}1/2H_2CO_3$)를 이용하여 부산물을 최소화시킨 고순도, 고수율로 합성하였으며, 이때 결정화 용매와 합성 과정에 따라 ${\alpha}$-form과 ${\beta}$-form을 각각 얻었다. 이들의 화학적 조성과 함량은 동일하지만, 구조적인 형태가 다르다는 것을 Raman-IR과 TGA-DSC 분석을 통해 관찰하였다. 특히 열특성(TGA-DSC)에 있어서 ${\alpha}$-form과 ${\beta}$-form 결정은 매우 큰 차이를 보였다. 흡열온도는 $100^{\circ}C$ 부근으로 유사한데 비하여, 발열최고온도에서는 ${\alpha}$-form은 $155.7^{\circ}C$이었으며, ${\beta}$-form은 $191.6^{\circ}C$로 나타났다. 또한 발열량도 ${\alpha}$-form은 536.4 J/g이었으나, ${\beta}$-form은 1310 J/g으로 2.5배 가까이 증가하는 형태를 나타냈다. 특히 열분해되는 패턴이 ${\alpha}$-form은 1단계 분해과정을 거치면서 급격히 질량이 감소하는 반면, ${\beta}$-form은 2단계 분해과정을 보이며 서서히 질량이 감소하는 특성이 관찰되었다.

Keywords

References

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