新型含能黏合剂研究进展及发展趋势

固体推进剂用的黏合剂多为一种含有活性官能团的高分子液态预聚物,它是构成固体推进剂弹性的基体,是推进剂核心组成中一个关键组分。含能黏合剂因可以改善氧化剂和金属燃烧剂的燃烧环境,释放更多的能量,提高推进剂的性能,近年来备受关注。阐述了近年来国内外在新型含能黏合剂方面的研究进展,对含能黏合剂的发展趋势进行了展望。     

高能推进剂钝感含能材料研究现状

钝感高能推进剂是当前固体推进剂的重要发展方向,降低高能固体推进剂感度主要技术途径是要采用低感度高能量的原材料,一方面是应用新型低感度含能原材料,另一方面是对现有含能原材料改性使之降低感度。高能推进剂所用钝感含能原材料主要分为3部分:能量高而感度低的氧化剂,低感度的含能黏合剂,低感度的含能增塑剂。在推进剂配方研制过程中通过选择应用这3类原材料来降低高能固体推进剂的感度,满足高能固体推进剂的钝感安全性能。论述了国内外上述3类钝感含能原材料的研究进展。     

固体推进剂用含能黏合剂体系研究进展

黏合剂含能化是近年来推进剂研究的热点之一，对叠氮基黏合剂和硝酸酯增塑聚醚黏合剂体系的制备、燃烧性能和能量性能进行了简要总结，并对今后黏合剂的发展做了展望。     

BAMO-AMMO黏合剂相对分子质量对推进剂力学性能的影响

ETPE(含能热塑性弹性体)具有力学性能好、能量大和不敏感等特性,因而已成为近年来国内外推进剂用黏合剂的理想基体。以BAMO-AMMO(3,3-二叠氮甲基氧杂环丁烷/3-甲基-3-叠氮甲基氧杂环丁烷嵌段共聚物)作为ETPE,制备了固体推进剂用黏合剂,并着重探讨了BAMO-AMMO黏合剂的Mr(相对分子质量)对推进剂力学性能、动态力学性能和微观结构等影响。研究结果表明:随着黏合剂Mr的增加,推进剂的高温拉伸强度、低温断裂伸长率、储能模量和弹性等均随之增大,而Tg(玻璃化转变温度)降低;然而,当黏合剂Mr过高时,推进剂复合体系中易出现分层现象。     

降低固体推进剂燃速研究进展

综述了复合推进剂、硝酸酯增塑聚醚(NEPE)推进剂和改性双基推进剂在降低燃速方面的研究进展,并指出未来降低固体推进剂燃速研究的重点为向推进剂中引入含能降速剂及采用热分解温度较高且能量较高的新型含能材料。     

固体含能材料与液体推进剂复合工艺概述

简述了液体火箭发动机难以仅通过优化其结构设计来进一步提高其比冲性能的现状,指出较经济且有效地提高比冲的方法是以现有液体火箭发动机为载体,向常规液体推进剂中添加含能材料,研制高能复合液体推进剂,提高比冲并改善其综合性能。通常添加的含能材料包括固体和液体。主要介绍固体含能材料与液体推进剂的复合工艺,并对不同复合工艺的适用范围进行分析和对比。     

BuNENA含能增塑剂的性能及应用

BuNENA(N–丁基硝氧乙基硝胺)是一种性能优良的新型含能增塑剂,在枪炮发射药和火箭推进剂应用中均受到研究者的广泛关注,并被进行系统研究。在发射药中,BuNENA具有塑化能力强、工艺性能好、感度低、能量高等优点,能进一步提高配方力学性能,其应用前景广阔。而在HTPE(端羟基聚环氧乙烷–四氢呋喃嵌段共聚醚)火箭推进剂中,BuNENA已被证明是一种对提高能量、降低感度和提高推进剂力学性能等具有明显作用的新型含能增塑剂,使用HTPE/BuNENA黏合剂体系的钝感固体推进剂的综合性能优于HTPB/AP(端羟基聚丁二烯/高氯酸铵)推进剂,并可满足钝感弹药(IM)要求,已在各种战术发动机中获得了实际应用。     

热塑性弹性体黏合剂在固体推进剂中的应用研究进展

介绍了热塑性弹性体(TPE)作为固体推进剂用黏合剂的特点、分类[如不含能热塑性弹性体、含能热塑性弹性体(ETPE)]和应用,重点综述了ETPE中聚叠氮缩水甘油醚(GAP)基和3,3-双(叠氮甲基)氧杂环丁烷(BAMO)基ETPE在推进剂中的研究进展。最后展望了TPE作为固体推进剂用黏合剂的发展前景。     

固体推进剂中新型含能材料研究进展

提高能量是固体推进剂研发过程中一直追求的主要目标,配方中加入新型含能材料是提高推进剂能量水平最重要的技术途径。作者介绍了近年来国内外在含能粘合剂、含能氧化剂、含能增塑剂和新型燃料添加剂方面的研究进展,并提出了固体推进剂在含能材料方面的发展趋势。     

聚缩水甘油醚硝酸酯研究进展

综述了一种在新一代高能航天固体推进剂、战术发动机高能低特征信号推进剂和聚合物黏结炸药(PBX)等领域中备受关注的含能聚合物黏合剂——聚缩水甘油醚硝酸酯(PGN)黏合剂的合成、性能及应用研究进展。     

聚叠氮缩水甘油醚的合成与改性研究进展

聚叠氮缩水甘油醚(GAP)是国内外重点研究的含能粘合剂之一。该文综述了GAP的合成研究进展,重点介绍了高相对分子质量GAP、支化GAP和等规GAP的合成。针对GAP反应活性低的特点,介绍了GAP的多种端基改性方法。GAP的无规、嵌段共聚物改善了GAP粘合剂的性能,GAP与其他粘合剂的互穿及共混,为GAP在推进剂中的应用提供了广阔前景。引用文献37篇。     

Development of Composite Solid Propellant Based on Nitro Functionalized Hydroxyl‐Terminated Polybutadiene

This paper presents an overview of a modified composite propellant formulation to meet future requirements. The composite propellant mixtures were prepared using nitro functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) as a novel energetic binder and addition of energetic plasticizer. The new propellant formulation was characterized and tested. It was found that the Nitro‐HTPB propellant with and without energetic plasticizer exhibited high solid loading, high density, and reasonable mechanical properties over a wide range of temperatures. It was shown that the burning rate of Nitro‐HTPB propellant is up to 40% faster than that of the HTPB propellant. These results are encouraging and suggest that it should be possible to improve the ballistic performance of popular HTPB propellants through use of the studied Nitro‐HTPB binder.     

固体推进剂用粘合剂研究进展

介绍了固体推进剂用粘合剂的研究进展,着重介绍了丁羟类、叠氮类、HTPE、NEPE以及硝基和硝酸酯类粘合剂的合成、工艺以及性能研究情况,并对未来固体推进剂用粘合剂的发展进行了展望。     

绿色固体推进剂的研究现状及展望

综述了无铅双基系推进剂、可再生TPE推进剂和绿色复合推进剂的研制现状,总结了各类绿色推进剂的特点和发展过程中的技术难题,指出了绿色推进剂的一些技术发展方向,如非铅催化剂的纳米化技术、高效负载技术和复合技术,含能热塑性弹性体的合成及应用技术,硝仿肼(HNF)提纯技术以及新型高能氧化剂合成技术等.     

Synthesis,Characterization and Thermal Properties of Poly(glycidyl azide‐r‐3‐azidotetrahydrofuran) as Azido Binder for Solid Rocket Propellants

Azido polymers have been investigated as energetic binders in the area of solid rocket propellants. However, the low temperature mechanical properties of them are not comparable with the traditional propellant binders. In this work, a new kind of azido binder named poly (glycidyl azide‐r‐3‐azidotetrahydrofuran) (PGAAT) was successfully synthesized. The molecular structures of monomers and copolymers were characterized. The sensitivity and thermal properties of the azido binder were studied. The cationic copolymerization of 3‐methylsulfonyloxytetrahydrofuran with ternary cyclic ethers was confirmed. The PGAAT azido binder exhibited attractive features like low glass transition temperature (T_g, −60 °C) and high energy (1798 J/g). The results indicate that the polymer is a suitable candidate binder for the solid rocket propellants.     

含能黏合剂聚缩水甘油醚硝酸酯合成研究进展

聚缩水甘油醚硝酸酯(PGN)是一种高能、钝感、洁净的富氧黏合剂。从20世纪50年代开始,它就一直是国外重点研究的高能固体推进剂含能黏合剂之一,也是近年来应用于推进剂、火炸药和烟火剂中的最具应用前景的含能黏合剂。以时间为序,分3个阶段较为详细地介绍了国内外PGN合成研究进展,指出了各个时期PGN合成工艺的优缺点。     

利用选择性溶解法研究NEPE推进剂的微观结构

为探索NEPE复合固体推进剂的微观结构特征，了解各组分在推进剂中的微观形态，对NEPE复合固体推进剂在水和三氯甲烷中的溶解过程进行了现象观测，得到了质量损失及离子浓度变化数据。用扫描电子显微镜对溶解剩余物进行了形貌观测。结果表明，NEPE推进剂中的黏合剂把固体颗粒粘结在一起。从微观结构上看NEPE推进剂比较致密，水和三氯甲烷都只能以渗透方式缓慢进入。推进剂中黏合剂的交联程度不高，未交联的黏合剂很容易被溶解；黏合剂受力伸长时包覆在其中的固体颗粒易脱离出来。     

Burning Rate – Pressure Relationship of NG‐PE‐PCP‐based High Energy Propellants

Nitramines are known to produce lower burning rates and higher pressure exponent (η) values. Studies on the burning rate and combustion behavior of advanced high‐energy NG/PE‐PCP/HMX/AP/Al based solid propellant processed by slurry cast route were carried out using varying percentages of HMX and AP. It was observed that propellant compositions containing only AP and Al loaded (total solids 75 %) in NG plasticized PE‐PCP binder produce comparatively lower pressure exponent (η) values similar to AP‐Al filled HTPB based composite propellants. However, energetic propellants containing high level of nitramine (40–60 %) produce high pressure exponent (0.8–0.9) values in the same pressure range. Incorporation of fine particle size AP (ca. 6 μm) and change in its concentration in the propellant composition reduces η value marginally and influences the burning rate. However, such compositions have higher friction sensitivity.     

Neutral Polymeric Bonding Agents (NPBA) and Their Use in Smokeless Composite Rocket Propellants Based on HMX‐GAP‐BuNENA

Very few efficient bonding agents for use in solid rocket propellants with nitramine filler materials and energetic binder systems are currently available. In this work, we report the synthesis, detailed characterization, and use of neutral polymeric bonding agents (NPBA) in isocyanate‐cured and smokeless composite rocket propellants based on the nitramine octogen (HMX), the energetic binder glycidyl azide polymer (GAP), and the energetic plasticizer N‐butyl‐2‐nitratoethylnitramine (BuNENA). These polymeric bonding agents clearly influenced the viscosity of the uncured propellant mixtures and provided significantly enhanced mechanical properties to the cured propellants, even at low NPBA concentrations (down to 0.001 wt‐% of propellant). A modified NPBA more or less free of hydroxyl functionalities for interactions with isocyanate curing agent provided the same level of mechanical improvement as regular NPBA containing a substantial number of reactive hydroxyl groups. However, some degree of reactivity towards isocyanate is essential for function.     

PGN——高能量密度固体推进剂含能组分

综述了聚缩水甘油醚硝酸酯(PGN)的性能、合成方法及应用研究。PGN是一种高密度、富氧的低感度含能黏合剂,兼有黏合剂和增塑剂作用,可用于大型运载火箭洁净推进剂、少烟推进剂及钝感PBX炸药。