【作者】 郭耸；

【导师】 孙金华；

【作者基本信息】 中国科学技术大学 ， 安全技术及工程， 2009， 博士

【摘要】 随着科技的进步和现代化工业水平的提高,人类为了满足各种需求,不断发现和生产出愈来愈多的新化学物质。这些物品中85%以上都属于危险化学品,一旦发生事故会给人民生命和财产造成严重威胁,甚至引发重大公共安全事故。危险化学品中危险性最高的一类物质即是爆炸性危险化学品,这类物质不仅在外界能量作用下能够发生火灾、爆炸等事故,而且在自然储存条件下也可能因为散热不当,热量积累引发自加速分解反应,最终导致爆炸。因此为了确保爆炸性危险化学品生产、储存和运输等过程中的热安全性,必须对这类物质的热分解特性进行充分细致的研究。本文选取了2种典型爆炸性危险化学品——双基发射药和混合硝酸酯发射药作为研究对象,使用了C80微量量热仪、热重-红外光谱联用仪（TG-FTIR）、气相色谱-质谱联用仪（GC/MS）等设备,从以下三个方面对它们的热分解特性展开研究,分别为:①双基发射药和混合硝酸酯发射药自身热分解特性;②外界因素对其热分解特性的影响;③过渡态金属化合物对混合硝酸酯发射药热分解特性的影响。在两种发射药自身热分解特性研究方面,通过等速升温实验观察了两种发射药的热分解行为,使用定温热分析动力学方法确定了两种发射药的缓慢热分解反应机理函数,同时还运用单一扫描速率非定温热分析方法计算了两种发射药的热分解动力学和热力学参数。文中还使用TG-FTIR和GC/MS研究了两种发射药热分解过程中气态产物的变化规律。最后,根据各种研究结论详尽地阐述了两种发射药的热分解过程,进一步揭示了均质发射药热分解的反应机理。在两种发射药受外界因素的影响研究方面,研究了实验药量、升温速率、水分含量、气氛、开闭环境等五种环境因素对两种发射药热分解特性的影响规律;计算了在各种环境因素影响下两种发射药的热分解反应动力学和热力学参数;对比观察了同一因素对两种发射药影响不同的现象,并对该现象给出了合理的解释。在过渡态金属化合物对混合硝酸酯发射药热分解特性的影响研究方面,研究了三氧化二铁（Fe₂O₃）等6种过渡态金属氧化物和铁酸镍（NiFe₂O₄）等5种过渡态金属有机酸盐对混合硝酸酯发射药热分解特性的影响规律,同时还研究了实验药量、环境压力等环境因素对含有Fe₂O₃、NiFe₂O₄的混合硝酸酯发射药热分解特性的影响规律。除上述研究工作外,本文还针对现有热分析方法方法的缺点,提出了一种基于C80微量量热仪实验的自催化反应动力学分析方法,该方法可以求解爆炸性危险化学品一级自催化反应两阶段的反应动力学参数,具有易于理解,求解过程简便,所需数量少等优点。更多还原

【Abstract】 With the development of technology,more new substances are found and produced to satisfy people’s requirements.85%of them can be grouped into hazardous chemicals,which can cause serious accidents on fire and explosion to endanger people’s life and property.In this kind of materials,the explosive hazardous chemicals are the most dangerous.Their accidents can be not only induced by external factor such as heat,impact,friction and so on,but also aroused by heat accumulation due to the poor capability of heat loss in the process of transportation and storage.Hence,in order to ensure thermal safety of the explosive hazardous chemicals,the research on thermal decomposition characteristics of these substances must be done adequately and carefully.In this paper,two typical explosive hazardous chemicals were selected,one is double base propellant,and the other one is multi-nitro ester propellant.And the researches were proceeded,using C80 calorimetry,TG-FTIR and GC/MS,from these three aspects:①Thermal decomposition behavior of double base propellant and multi-nitro ester propellant;②Influence of environmental factors on thermal decomposition characteristics of these two propellants;③Effect of transition-metal compounds on thermal decomposition characteristics of multi-nitro ester propellant.In the fist research topic,thermal decomposition behavior was observed under the constant heating rate experiment;the reaction mechanism function on slow thermal decomposition of these two propellants were obtained using thermal analysis method based on constant temperature kinetics;and the thermal decomposition kinetics parameters of these two propellants were calculated using thermal analysis method based on single constant heating rate kinetics.And the variation on gas product of thermal decomposition of these two propellants was studied by this work using TG-FTIR and GC/MS.At last,in this topic,according to the above results and previous work,the thermal decomposition steps of these two propellants were discussed,and then the thermal decomposition mechanism of these two propellants was revealed.In the second topic,the used environmental factors include the initial quantity of sample,heating rate,moisture content,open/closed system,and different atmospheres. The influences of these five factors on thermal decomposition characteristics of two propellants were researched by this topic.The thermal decomposition kinetics parameters of these two propellants were calculated and compared under these factors, using thermal analysis method based on single constant heating rate kinetics.The difference on thermal decomposition behavior between double base propellant and multi-nitro ester propellant under the initial quantity of sample,heating rate,or moisture content was found.And this phenomenon was explained reasonably.In the third topic,the influences of six transition-metal oxides,such as Fe₂O₃, and five transition-metal organic acid salts,such as NiFe₂O₄,on the thermal decomposition characteristics of multi-nitro ester propellant were researched by using C80 calorimetry.And the influences of initial quantity of sample and ambient pressure on the thermal decomposition characteristics of multi-nitro ester propellant with transition-metal compounds,including Fe₂O₃ and NiFe₂O₄,were analyzed in detail.Except for the above-mentioned works,a new autocatalytic kinetics method based on the experiments using C80 calorimetry,was devised in accordance with the deficiency of thermal kinetic methods available.According to this method,the thermal kinetic parameters on the two stages within first-order autocatalytic reaction of explosive hazardous chemicals can be calculated accurately.更多还原