Thesis Advisor张延强
Degree Grantor中国科学院研究生院
Degree Name硕士
Degree Discipline化学工程

推进剂是火箭和航天飞行器的动力核心,对航天事业发展起着至关重要的作用。传统的肼类推进剂具有毒性和致癌性,迫切需要开发绿色替代产品。自燃离子液体由于具有低熔点、宽液程、高热稳定性等特点,成为潜在的下一代推进剂燃料。点火延迟时间是评估燃料性能的重要参数,而大多数自燃离子液体点火活性较差。本文通过引入具有催化作用的金属离子,获得了一系列具有良好点火性能的自燃离子液体。具体内容如下:设计合成了六种[B12H12]2-类金属(Cu2+,Ni2+,Zn2+)配位化合物。测试分析表明,六种金属配合物在室温下均为固体,熔点为196.7-269.3 oC,这可能归因于它们高度对称的结构。在热稳定性方面,这些配合物的分解温度大于220 oC,其中[Ni(C5H6N2)6]B12H12的分解温度最高(286.3 oC)。此外,它们的密度优于肼类燃料(1.215-1.264 g cm-3),[Cu(C5H6N2)4]B12H12的密度最高(1.264 g cm-3)。点火测试的结果表明,[Cu(C5H6N2)4]B12H12和[Ni(C5H6N2)6]B12H12均展现出超短的点火延迟时间(1ms),且对于点火延迟时间的主要影响来自不同金属离子的催化作用。设计合成了五种N(CN)2-类Cu2+配位化合物。测试分析表明,五种配合物的熔点为57.5-133.6 oC,分解温度为200-282 oC,密度为1.10-1.31 g cm-3。其中,熔点和密度随着侧链长度的增加而逐渐减小。以1.0-5.0 %的不同比例将这些配合物添加到N(CN)2-基的自燃离子液体中,并测定它们的点火延迟时间。混合体系表现出更优的点火活性。例如,1-烯丙基-3-甲基咪唑二氰胺盐在没有加入任何添加剂之前展现出较差的点火活性(43 ms),而添加了质量分数5 %的[Cu(C6H8N2)4][N(CN)2]2添加剂的混合体系展现出短至6 ms的点火延迟时间。综上所述,本文在提高点火活性的指导思想下,得到了[B12H12]2-类金属(Cu2+,Ni2+,Zn2+)配位化合物和N(CN)2-类Cu2+配位化合物。对这些配合物的结构、相变温度、热稳定性、密度和点火活性进行了表征和充分讨论,证实了通过引入金属离子来提高点火活性的可行性。;Propellants are the core power for rockets and aerospacecrafts, whcih play a vital role in the development of space industry. The traditional fuels of hypergolic propellants such as hydrazine and its derivatives are toxic and carcinogenic, so that it is urgent to design the green alternatives. As the potential next-generation propellant fuels, hypergolic ionic liquids (HILs) have been recognized with low melting point, wide liquid range, high thermal stability, and so on. However, most of HILs possess undesired ignition delay times, which is a significant parameter in evaluating the fuels. Herein, a new family of hypergolic metal-cioordination ILs with superior hypergolicity were prepared by the addition of catalytic metal ions. The contents are as follows:Six B12H122--based metal (Cu2+, Ni2+, Zn2+) complexes were designed and prepared. The results showed that the six metal complexes are all solid at room temperature with melting points ranging from 196.7 to 269.3 oC, which is partly due to the structural symmetry. As to thermal stabilities, these complexes possessed decomposition temperatures > 220 oC, and [Ni(C5H6N2)6]B12H12 gave the highest decomposition temperatures of 286.3 oC. Their densities are all much higher than those of hydrazine-based fuels ranging from 1.215 to 1.264 g cm-3. Among them, [Cu(C5H6N2)4]B12H12 exhibited the highest density of 1.264 g cm-3. The results of hypergolic tests showed that [Cu(C5H6N2)4]B12H12 and [Ni(C5H6N2)6]B12H12 had ultra-short ignition delay times (1 ms), and the main contribution to the ignition delay times came from the favorable catalytic effect of metal ions.Five N(CN)2--based Cu2+ complexes were designed and prepared. The results showed that melting points of 57.5-133.6 °C, decomposition temperatures of 200-282 °C and densities of 1.10-1.31 g cm-3. Among them, melting points and densities decrease with the increase of the side chain length. These complexes were added to some N(CN)2--based HILs with the propotions ranging from 1.0-5.0 %. Their ignition delay times were measured, showing the desirable hypergolicity. For example, 1-allyl-3-methylimidazolium dicyanamide indicated the inferior hypergolicity (tid: 43 ms), while it gave a very fast ignition delay time as short as 6 ms after adding 5 % [Cu(C6H8N2)4][N(CN)2]2.In short, B12H122--based metal (Cu2+, Ni2+, Zn2+) complexes and N(CN)2--based Cu2+ complexes were obtained from the idea of enhancing hypergolicity. The structures, phase transition temperatures, thermal stabilities, densities and hypergolicity of these complexes were measured (or calculated), and fully dicussed. The results verified the feasibility of enhancing the HILs hypergolicity by the introduction of favorable metal ions.

Document Type学位论文
Recommended Citation
GB/T 7714
章泽筠. 金属配位自燃离子液体的合成及表征[D]. 中国科学院研究生院,2018.
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