摘要
为详细探究高氯酸铵基分子钙钛矿型含能材料(H_(2)dabco)(NH_(4))(ClO_(4))_(3)(DAP-4),/5,5′-联四唑-1,1′-二氧二羟铵(TKX-50)混合物的热分解特性(其中H_(2)dabcO_(2+)为1,4-二氮杂双环[2.2.2]辛烷-1,4-二鎓离子),采用差示扫描量热法-热重/质谱/傅里叶红外光谱联用技术对比分析了DAP-4、DAP-4/TKX-50混合物的热分解特性和气体产物,利用固体原位红外技术对DAP-4、DAP-4/TKX-50混合物凝聚相特征基团随温度的变化进行了研究,最后推测出了DAP-4/TKX-50混合物热分解机理。结果表明,DAP-4与TKX-50混合后,DAP-4对TKX-50的热分解影响较小,TKX-50热分解产生的热量使DAP-4可逆相变吸热峰消失,但几乎不影响其高温下的热分解;DAP-4/TKX-50混合物热质量损失分为2个阶段,第一阶段质量损失为43.4%,第二阶段质量损失为52.4%,分解残渣剩余4.2%;DAP-4热分解产生的气体产物主要有NH_(3)、H_(2)O、HNCO、HCN、CO、HCl和CO_(2),DAP-4/TKX-50混合物热分解产生的气体产物主要有H_(2)O、NO、N_(2)O、HCl、NH_(3)、N_(2)、HNCO、HCN、CO和CO_(2)。DAP-4/TKX-50混合物的热分解机理为:TKX-50分子内发生氢离子可逆转移,生成羟胺和1,1′-二羟基-5,5′联四唑(BTO);羟胺在高温下再继续分解为小分子气体,BTO分解产生的碎片部分聚合成偶联产物;最后,DAP-4离子键断裂,笼状骨架瞬间坍塌,强还原性和强氧化性气体组分在高温下发生剧烈氧化还原反应,并释放大量热。
To explore the detailed thermal decomposition properties of the mixture system consists of ammonium perchlorate-based molecular perovskite energetic material(H_(2)dabco)(NH_(4))(ClO_(4))_(3)(DAP-4,where H_(2)dabco_(2+)refers to 1,4-diazabicyclo[2.2.2]octane-1,4-dianiumion)and dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate(TKX-50),the thermal decomposition characteristics and gas products of DAP-4 and DAP-4/TKX-50 mixtures were comparatively analyzed by using differential scanning calorimetry-thermogravimetry/mass spectrometry/fourier infrared spectroscopy;meanwhile,the changes of characteristic groups in the condensed phase of DAP-4 and DAP-4/TKX-50 mixtures with temperature were investigated by in-situ FT-IR.Based on the explorations the thermal decomposition mechanism of DAP-4/TKX-50 mixture was proposed.The results showed that after mixing DAP-4 with TKX-50,DAP-4 had little effect on the thermal decomposition of TKX-50,while the heat generated by the thermal decomposition of TKX-50 made the reversible phase transition endothermic peak of DAP-4 disappeared,but hardly affected DAP-4′s thermal decomposition at high temperature.The thermal mass loss of DAP-4/TKX-50 mixture was divided into two stages.The mass loss of the first stage was 43.4%and the mass loss of the second stage was 52.4%,leaving 4.2%of the decomposition residue.The main gas products produced by thermal decomposition of DAP-4 and DAP-4/TKX-50 mixture were NH_(3)/H_(2)O/HNCO/HCN/CO/HCl/CO_(2)and H_(2)O/NO/N_(2)O/HCl/NH_(3)/N_(2)/HNCO/HCN/CO/CO_(2),respectively.The thermal decomposition mechanism of the DAP-4/TKX-50 mixture was proposed as follows:the reversible transfer of hydrogen ions occurs first in the molecule of TKX-50 to generate hydroxylamine and 1,1′-dihydroxy-5,5′-bitetrazole(BTO),then hydroxylamine decomposed into small molecular gases at high temperature while the fragments generated by BTO decomposition partially polymerized into coupling products.Finally,the ionic bond of DAP-4 was broken,leading to instantaneous collapse of the cage-like skeleton.The strongly reducing and strongly oxidizing gas components underwent violent redox reactions at high temperatures and release a large amount of heat.
作者
张坤
冯博
王晓峰
尚宇
席鹏
潘文
冯晓军
ZHANG Kun;FENG Bo;WANG Xiao-Feng;SHANG Yu;XI Peng;PAN Wen;FENG Xiao-jun(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2022年第7期673-680,共8页
Chinese Journal of Energetic Materials
基金
国家自然科学基金(U2141202)。
