摘要
为研究螺杆泵送和中深孔装药时伴随的高压作用对现场混装乳化炸药基质微观结构和热稳定性的影响,采用光学显微镜、激光粒度仪、水溶性实验、热重与微商热重联用技术、Kissinger法和Ozawa法、Coats-Redfern法和?atava法,对常压、高压环境下基质的微观结构、粒径分布、析晶含量、热分解过程、热分解反应活化能、热分解机理函数和速率方程进行了研究。结果表明,从常压到高压,基质内相液滴出现聚合、破乳、析晶现象,粒径由3.717μm增大为4.474μm,硝酸铵晶体的析出量由0.0530 g增大为0.0640 g,乳液体系均一性减弱;基质的平均热分解起始温度T_(onset)由157.4℃升高为184.0℃,平均一阶微商热重峰温T_(p)由262.6℃升高为281.8℃,平均质量损失平均速率由0.1454%·s^(-1)升高为0.1476%·s^(-1),反应活化能由108.49 k J·mol^(-1)降低为84.74 k J·mol^(-1),高压下蒸发破乳释放的游离水可能造成了T_(onset)与T_(p)上升,热分解反应更容易发生;Ozawa法计算的活化能随着转化率增大的变化趋势不同,热分解反应的机理函数从Valensi方程变为反Jander方程,其速率方程也发生了变化。高压作用促进了基质内相液滴聚合、破乳、析晶过程,降低了热分解反应发生的活化能,减弱了体系均一性、热稳定性。
In order to study the effect of high pressure from screw pumping and medium deep hole charging on the microstructure and thermal stability of the on-site mixed emulsion explosive matrix,the microstructure,particle size distribution,crystallization content,thermal decomposition process,thermal decomposition reaction activation energy,thermal decomposition mechanism function and rate equation of the matrix under atmospheric and high pressures were studied by optical microscope,laser particle size analyzer,water solubility experiment,thermogravimetry and derivative thermogravimetry(TG-DTG)couple method,Kiss-inger method and Ozawa method,Coats-Redfern method andŠatava method.The results show that from atmospheric pressure to high pressure,polymerization,demulsification and crystallization of the intra-matrix phase droplets appeared,the particle size increased from 3.717μm to 4.474μm,the precipitation amount of ammonium nitrate crystals increased from 0.0530 g to 0.0640 g,and the uniformity of the emulsion system was weakened.The average thermal decomposition onset temperature of the matrix Tonset increased from 157.4℃to 184.0℃,the average first-order derivative thermogravimetric peak temperature Tp in-creased from 262.6℃ to 281.8℃,the average mass loss rate increased from 0.1454%·s^(-1) to 0.1476%·s^(-1),and the reaction ac-tivation energy decreased from 108.49 kJ·mol^(-1) to 84.74 kJ·mol^(-1).The free water released by evaporative demulsification under high pressure might cause the rise of Tonset and Tp,and the thermal decomposition reaction was more likely to occur.The activa-tion energy calculated by the Ozawa method had a different trend with the increase of conversion rate,and the thermal decom-position reaction mechanism function changed from Valensi equation to inverse Jinder equation and the rate equation also changed.The high pressure promotes the process of droplet polymerization,demulsification and crystallization of the intra-matrix phase,reduces the activation energy of the thermal decompo
作者
潘长鑫
刘锋
毕如洁
代伟
朱正德
程雨航
PAN Chang-xin;LIU Feng;BI Ru-jie;DAI Wei;ZHU Zheng-de;CHENG Yu-hang(School of Chemical Engineering,Anhui University of Science and Technology,Huainan 232001,China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2024年第10期1080-1090,共11页
Chinese Journal of Energetic Materials
基金
国家自然科学基金(51134012,51776010)。
关键词
高压作用
现场混装
乳化基质
微观结构
热分解动力学
high-pressure effect
on-site mixed assembly
emulsified matrix
microstructure
thermal decomposition kinetics
