膨化硝酸铵自敏化理论及其炸药的物理性能和改性研究
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摘要
本文对不同粒径的膨化硝酸铵和普通粉状硝酸铵的孔径分布、孔容、累积孔面积和孔体积、扩展表面积和吸附能力等表面特性参数进行了系统测定，测试结果可以从微观上解释了膨化硝酸铵比普通粉状硝酸铵具有较高的吸油率和较低渗油性的根本原因在于膨化硝酸铵的多微孔结构特征。测试表明粉碎并不会破坏膨化硝酸铵的微细孔，也在一定程度上验证了自敏化理论的正确性。在分析热点理论和热爆炸理论的基础上，结合表面特性参数测试结果和膨化工艺的影响，提出了膨化硝酸铵及其炸药在热点形成时具有随机性；对膨化铵油炸药的冲击波感度进行了测试，表明膨化硝酸铵具有较高的冲击波感度，较大的比表面积和孔隙率完全符合冲击起爆的条件，从冲击波感度方面验证了自敏化理论的正确性。
利用双谱线测温技术建立了一套光纤测温系统，对膨化硝铵炸药、铵梯类炸药、乳化炸药和粉状乳化炸药的爆炸瞬态温度进行了实时连续测量，获得了几类炸药的爆温随时间的变化结果，测试结果表明膨化硝铵炸药具有较高的爆温，根据爆温测试结果，利用人工神经网络法优选了岩石和煤矿膨化硝铵炸药的配方。利用绝热法测试数种膨化硝铵炸药的爆热，结果表明膨化硝铵炸药具有较高的爆热。从爆温和爆热两个能量指标上证明了自敏化理论的正确性。
采用加速量仪研究了膨化硝酸铵及其炸药、普通硝酸铵、铵梯类炸药、乳化炸药和粉状乳化炸药的绝热分解过程；利用速率常数法和机理函数法计算了绝热分解的活化能、指前因子、反应级数等动力学参数和反应热等热力学参数。从绝热分解过程的温度、压力和温升速率随时间的变化，对膨化硝酸铵及其炸药和其它几类炸药的热安定性进行了安全性评价。测试表明膨化硝酸铵及其炸药和其它几类炸药具有良好的热安全性。
针对膨化硝铵炸药的流散性问题，采用添加流散性好的非爆炸性固体粉末、调整油相组成和配比以及用具有较高燃热值的固体可燃剂代替柴油的方法来改进膨化硝铵炸药的流散性，取得了丰富的实验结果，并提出了判断流散性的方法。针对装药密度问题，采用了在膨化过程中添加膨化结晶改性剂的方法和用部分微细粉状硝酸铵代替膨化硝酸铵的方法来改善装药密度的问题，实验表明两种方法是可行的，可提高装药密度。
本文采用纤维化、氧化剂盐浸泡法和包覆催化法对木粉进行了改性研究，并研究了改性木粉对炸药爆炸性能的影响，三种改性方法都能使膨化硝铵炸药的爆炸性能得到提高。对纤维化木粉、氧化剂盐改性木粉和不同粒度的普通木粉的表面特性参数进行了测试，表明两种改性木粉提高炸药爆炸性能的机理不同。不同粒度的普通木粉的表面特性参数相差不大，不再是决定炸药性能的关键因素，而粒度成为决定性因素。测试结果为木粉具有敏化、疏松作用提供了直接的证据。
In this dissertation, the pore diameter distribution, pore volume, cumulative pore area and pore volume, extended surface area, specific surface area and adsorbability of expanded ammonium nitrate and powdery ammonium nitrate have been measured respectively. It is shown from measurement that the reason of expanded ammonium nitrate possessing higher oil adsorbability and lower oil effusion than that of powdery ammonium nitrate lies in its micro-porous structure. It is also shown that micro-pore couldn't be destroyed by crush. Based on theory of hot spot and thermal explosion, and combined the measurement results and influences of expansion process, randomicity of hot spot formation in expanded ammonium nitrate and its explosives is proposed. Sensitivity to shock 'wave of expanded ammonium nitrate fuel oil explosives have been tested, it is concluded that expanded ammonium nitrate fuel oil explosives have higher shock wave sensitivity, expanded ammonium nitrate has larger specific surface area and porousity me
t the shock initiation mechanism requirement. It is proven from these measurements that the theory of self-sensitization of ammonium nitrate is correct.
Based on double spectra line temperature measurement method, a set of optical fiber temperature measurement system has been established. Detonation temperature of expanded ammonium nitrate explosive, AN-TNT type explosive, emulsion explosive and powdery emulsion explosive have been measured real time and continuously, using this system, and temperature-time distribution results are obtained. It is concluded that expanded ammonium nitrate explosive possess higher detonation temperature. Formulas of rock and permissible expanded ammonium nitrate explosive are determined by annual neural net method, according to temperature measurement results. Detonation heat of expanded ammonium nitrate explosive also has been tested by adiabatic method. It is shown that expanded ammonium nitrate explosive has higher detonation heat. From two energy index, namely, detonation temperature and detonation heat, it is proved that self-sensitization theory is reasonable and right.
Adiabatic thermal decomposition of expanded ammonium nitrate and its explosive, AN-TNT type explosive, emulsion explosive and powdery emulsion explosive have been investigated using accelerating rate calorimetry. Kinetic parameters, such as activation energy, pre-exponential factor and reaction order and reaction heat are calculated using reaction rate method and mechanism function method. Thermal safety of expanded ammonium nitrate and its explosive, and other type explosive have been evaluated according to temperature, pressure and temperature rise rate in thermal decomposition. It is revealed that expanded ammonium nitrate and its explosive, and other type explosive is thermal stable.
To the question of poor fluidity of expanded ammonium nitrate explosive, three methods are introduced to solve this problem. One is non-explosion powder materials with better fluidity are added in explosive, another is regulating the oil composition and formula, last method is that diesel is substituted by solid combustible agent with higher combustion heat value. Satisfactory and plenty results are obtained, and estimation methods of fluidity are proposed in this dissertation. In order to improve charge density of expanded ammonium nitrate explosive, crystal modification agents are used in expansion process, and part of expanded ammonium nitrate are replaced by powder ammonium nitrate, two methods are feasible and can improve charge density.
Fibrosis method, oxidizer salts soakage method and coating catalystic method are introduced to modify sawdust, and influences of modified sawdust on explosion properties are also investigated, three kinds of modified sawdust are feasible in improving explosion properties of expanded ammonium nitrate explosive. Surface characteristic parameters of fibrosis sawdust, oxidizer salts sawdust and ordinary sawdust of different particle size are measured, it is revealed
that the mechanism o
利用双谱线测温技术建立了一套光纤测温系统，对膨化硝铵炸药、铵梯类炸药、乳化炸药和粉状乳化炸药的爆炸瞬态温度进行了实时连续测量，获得了几类炸药的爆温随时间的变化结果，测试结果表明膨化硝铵炸药具有较高的爆温，根据爆温测试结果，利用人工神经网络法优选了岩石和煤矿膨化硝铵炸药的配方。利用绝热法测试数种膨化硝铵炸药的爆热，结果表明膨化硝铵炸药具有较高的爆热。从爆温和爆热两个能量指标上证明了自敏化理论的正确性。
采用加速量仪研究了膨化硝酸铵及其炸药、普通硝酸铵、铵梯类炸药、乳化炸药和粉状乳化炸药的绝热分解过程；利用速率常数法和机理函数法计算了绝热分解的活化能、指前因子、反应级数等动力学参数和反应热等热力学参数。从绝热分解过程的温度、压力和温升速率随时间的变化，对膨化硝酸铵及其炸药和其它几类炸药的热安定性进行了安全性评价。测试表明膨化硝酸铵及其炸药和其它几类炸药具有良好的热安全性。
针对膨化硝铵炸药的流散性问题，采用添加流散性好的非爆炸性固体粉末、调整油相组成和配比以及用具有较高燃热值的固体可燃剂代替柴油的方法来改进膨化硝铵炸药的流散性，取得了丰富的实验结果，并提出了判断流散性的方法。针对装药密度问题，采用了在膨化过程中添加膨化结晶改性剂的方法和用部分微细粉状硝酸铵代替膨化硝酸铵的方法来改善装药密度的问题，实验表明两种方法是可行的，可提高装药密度。
本文采用纤维化、氧化剂盐浸泡法和包覆催化法对木粉进行了改性研究，并研究了改性木粉对炸药爆炸性能的影响，三种改性方法都能使膨化硝铵炸药的爆炸性能得到提高。对纤维化木粉、氧化剂盐改性木粉和不同粒度的普通木粉的表面特性参数进行了测试，表明两种改性木粉提高炸药爆炸性能的机理不同。不同粒度的普通木粉的表面特性参数相差不大，不再是决定炸药性能的关键因素，而粒度成为决定性因素。测试结果为木粉具有敏化、疏松作用提供了直接的证据。
In this dissertation, the pore diameter distribution, pore volume, cumulative pore area and pore volume, extended surface area, specific surface area and adsorbability of expanded ammonium nitrate and powdery ammonium nitrate have been measured respectively. It is shown from measurement that the reason of expanded ammonium nitrate possessing higher oil adsorbability and lower oil effusion than that of powdery ammonium nitrate lies in its micro-porous structure. It is also shown that micro-pore couldn't be destroyed by crush. Based on theory of hot spot and thermal explosion, and combined the measurement results and influences of expansion process, randomicity of hot spot formation in expanded ammonium nitrate and its explosives is proposed. Sensitivity to shock 'wave of expanded ammonium nitrate fuel oil explosives have been tested, it is concluded that expanded ammonium nitrate fuel oil explosives have higher shock wave sensitivity, expanded ammonium nitrate has larger specific surface area and porousity me
t the shock initiation mechanism requirement. It is proven from these measurements that the theory of self-sensitization of ammonium nitrate is correct.
Based on double spectra line temperature measurement method, a set of optical fiber temperature measurement system has been established. Detonation temperature of expanded ammonium nitrate explosive, AN-TNT type explosive, emulsion explosive and powdery emulsion explosive have been measured real time and continuously, using this system, and temperature-time distribution results are obtained. It is concluded that expanded ammonium nitrate explosive possess higher detonation temperature. Formulas of rock and permissible expanded ammonium nitrate explosive are determined by annual neural net method, according to temperature measurement results. Detonation heat of expanded ammonium nitrate explosive also has been tested by adiabatic method. It is shown that expanded ammonium nitrate explosive has higher detonation heat. From two energy index, namely, detonation temperature and detonation heat, it is proved that self-sensitization theory is reasonable and right.
Adiabatic thermal decomposition of expanded ammonium nitrate and its explosive, AN-TNT type explosive, emulsion explosive and powdery emulsion explosive have been investigated using accelerating rate calorimetry. Kinetic parameters, such as activation energy, pre-exponential factor and reaction order and reaction heat are calculated using reaction rate method and mechanism function method. Thermal safety of expanded ammonium nitrate and its explosive, and other type explosive have been evaluated according to temperature, pressure and temperature rise rate in thermal decomposition. It is revealed that expanded ammonium nitrate and its explosive, and other type explosive is thermal stable.
To the question of poor fluidity of expanded ammonium nitrate explosive, three methods are introduced to solve this problem. One is non-explosion powder materials with better fluidity are added in explosive, another is regulating the oil composition and formula, last method is that diesel is substituted by solid combustible agent with higher combustion heat value. Satisfactory and plenty results are obtained, and estimation methods of fluidity are proposed in this dissertation. In order to improve charge density of expanded ammonium nitrate explosive, crystal modification agents are used in expansion process, and part of expanded ammonium nitrate are replaced by powder ammonium nitrate, two methods are feasible and can improve charge density.
Fibrosis method, oxidizer salts soakage method and coating catalystic method are introduced to modify sawdust, and influences of modified sawdust on explosion properties are also investigated, three kinds of modified sawdust are feasible in improving explosion properties of expanded ammonium nitrate explosive. Surface characteristic parameters of fibrosis sawdust, oxidizer salts sawdust and ordinary sawdust of different particle size are measured, it is revealed
that the mechanism o
引文
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4 吕春绪，刘祖亮，惠君明．膨化硝酸铵自敏化理论形成与发展．火炸药学报，2000，23(4)：1～4
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2 陈天云．硝酸铵的自敏化及其应用研究：[学位论文]．南京：南京理工大学，2000．10
3 陆明．膨化硝铵炸药研究：[学位论文]．南京：南京理工大学，1999．7
4 吕春绪，刘祖亮，惠君明．膨化硝酸铵自敏化理论形成与发展．火炸药学报，2000，23(4)：1～4
5 叶志文．硝酸铵膨化机理研究．[学位论文]．南京：南京理工大学，1995
6 陆明．吕春绪，刘祖亮膨化硝酸铵的膨化过程研究．火炸药学报．1999，22(3)：15～18
7 陆明，吕春绪，刘祖亮．硝酸铵膨化过程中的结晶参数研究．含能材料，1999，(2)：79
8 叶志文，吕春绪，刘祖亮．混合表面活性剂在饱和硝酸铵溶液中的物化性质．南京理工大学学报，1999，(2)：166
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