化学学报 ›› 2012, Vol. 70 ›› Issue (02): 200-206.DOI: 10.6023/A1109253 上一篇    下一篇

研究论文

新型含能纤维素基凝胶推进剂的流变性能研究

吕少一, 邵自强, 张振玲, 王慧庆, 王文俊   

  1. 北京理工大学材料科学与工程学院 北京 100081
  • 收稿日期:2011-09-25 修回日期:2011-11-30 出版日期:2012-01-28 发布日期:2012-02-25
  • 通讯作者: 邵自强 E-mail:shaoziqiang@263.net
  • 基金资助:

    燃烧与爆炸国防科技重点实验室基金(No.9140C3503011004)资助项目.

Studies on Rheological Properties of Gelled Propellant Based on New Energetic Cellulose

Lü Shaoyi, Shao Ziqiang, Zhang Zhenling, Wang Huiqing, Wang Wenjun   

  1. School of Materias Science and Engineering, Beijing Institute of Technology, Beijing 100081
  • Received:2011-09-25 Revised:2011-11-30 Online:2012-01-28 Published:2012-02-25
  • Supported by:

    Project supported by Combustion and Explosion National Defense Key Laboratory Fund (Grant No.9140C3503011004).

制备了以羧甲基纤维素硝酸酯(CMCN)为胶凝剂的硝基甲烷(NM)凝胶, 系统研究了CMCN 修饰基团比例变化所引起NM/CMCN凝胶流变性能差异性的规律. 探讨了凝胶的形成机理并采用线性的流变学方法研究了NM/CMCN凝胶的屈服性、触变性、蠕变性、温敏性等动态粘弹性质, 分别利用Herschel-Bulkley 模型、Burger 模型、Carreau-Yasuda模型、Andrade-Eyring 模型对凝胶的流动曲线、蠕变曲线、频率曲线和温敏曲线进行了数据拟合. 研究发现, NM/CMCN凝胶是由CMCN 大分子链上两亲性基团与有机小分子基团间通过分子链间疏水键、氢键等非共价键相互作用形成的一种物理交联网络型凝胶. 凝胶的非牛顿系数n均小于0.60. 随着硝酸酯基团含量的减少, NM/CMCN 凝胶的结构强度变弱, 表现出屈服应力逐渐减小、触变恢复性逐渐增强、粘性与弹性柔量均减小但粘性柔量比例增加的趋势; 凝胶的弹性响应性逐渐减弱而粘性响应性渐强, 内耗也逐渐增大;凝胶的活化能总体上增大, 温度稳定性变弱.

关键词: 含能胶凝剂, 羧甲基纤维素硝酸酯, 硝基甲烷, 流变性, 凝胶推进剂

The nitromethane (NM) gels was prepared with carboxymethyl cellulose nitrate (CMCN) as a gelator. The law of different rheological properties of NM/CMCN gels caused by the proportional change of modified group on CMCN was investigated. The yield stress, thixotropy, creep and thermosensitivity of NM/CMCN gels were investigated by linear rheological methods and the gel mechanism was discussed. The flow data, creep data, angular frequency data and thermosensitivity data of gels were fitted by Herschel-Bulkley model, Burger model, Carreau-Yasuda model and Andrade-Eyring model respectively. The experimental results show that NM/CMCN gel is a physical gel with a crosslinking network structure which is formed by non-covalent interaction of hydrophobic bonds and interchain hydrogen bonds between amphiphilic group along the macromolecular chain of CMCN and small organic molecules. The non-Newton coefficient n of CMCN gels are all less than 0.60. With the decrease of the content of nitrate group, structure strength of NM/CMCN gels become weaker, therefore, the yield stress decrease while thixotropy recovery increase gradually, the viscous compliance and elastic compliance of gel decrease while the proportion of viscous compliance increase. The elastic responsivity decreases while viscous responsivity increase, and the internal friction increases gradually. The activation energy of NM/CMCN gels increase from the global aspect and temperature stability become weaker with the decrease of the content of nitrate group.

Key words: energetic gelator, carboxymethyl cellulose nitrate, nitromethane, rheological property, gelled propellant