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。     

GAP基含能热塑性弹性体制备及其在复合固体推进剂中的应用进展

介绍了含能热塑性弹性体(ETPE)的概念及制备方法,分析了复合固体推进剂用ETPE的特点,综述了GAP(聚叠氮缩水甘油醚)基含能热塑性弹性体及GAP基热塑性推进剂的研究进展,针对GAP基ETPE在热塑性推进剂应用中存在的问题,提出了可能的解决方法,认为GAP基ETPE作为黏合剂将会是热塑性推进剂的一个发展方向。     

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。     

黏合剂和钝感RDX对ETPE发射药流变性能的影响

以不同Mn(数均相对分子质量)的ETPE(含能热塑性弹性体)为黏合剂、不同粒度的RDX(黑索今)为含能添加剂,制备了一种PBX(聚合物粘接炸药)——ETPE发射药。研究结果表明:ETPE发射药的表观黏度(η)随剪切应力和温度的升高而降低,较高的压力和温度有利于发射药的流动变形,加工温度以90~95℃为宜;当温度和RDX粒度相同时,ETPE的Mn越小,ETPE发射药的η越低;当温度和ETPE的Mn相同时,RDX的粒度越大,ETPE发射药的η越低。     

GAP基热塑性弹性体的合成与表征

以聚叠氮缩水甘油醚(GAP)、亚甲基二苯基二异氰酸酯(MDI)、1,4-丁二醇(BDO)为原料,采用两步法合成了一种GAP基的含能热塑性弹性体(ETPE).用差示扫描量热(DSC)、傅里叶变换红外光谱(FT-IR)、热失重(TG)和万能材料拉伸机等对ETPE进行了表征.结果表明,ETPE具有良好的低温性能和热稳定性,高...     

GAP-ETPE基发射药配方的能量特性分析

采用内能法计算了GAP含能热塑性弹性体(ETPE)为基的多个发射药配方的能量特性参数.结果表明,RDX/ETPE/A3发射药的火药力约为1 170 kJ/kg,用CL-20、TNAZ等替代配方中的RDX,火药力呈线性规律变化,并且能够得到1 300 kJ/kg以上的火药力.不同的含能增塑剂对配方的能量有很大的影响,含BTTN、BuNENA发射药配方具有很高的能量,RDX/ETPE/NC/BTTN(ETPE与NC的质量比为70∶30)发射药配方的火药力在较宽的范围内都可以达到1 200 kJ/kg.     

GAP基含能热塑性弹性体的合成与表征

以聚叠氮缩水甘油醚(GAP)为软段,1,4-丁二醇(BDO)和4,4′-二苯基甲烷二异氰酸酯(MDI)为硬段,采用熔融预聚体法合成了GAP基含能热塑性弹性体(ETPE)。研究了扩链剂加料方式、催化剂用量、异氰酸酯指数、硬段含量等因素对弹性体力学性能的影响。采用傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)、热台显微镜、差示扫描量热(DSC)、热重分析(TG)表征了ETPE的性能。结果表明,采用恒速滴加扩链剂方法合成的ETPE具有良好的热稳定性和力学性能。当催化剂质量分数为0.6‰,异氰酸酯指数(R)为0.98,硬段质量分数(Y)为35%时,热塑性弹性体的数均相对分子质量为52 312,软化点为96℃,拉伸强度为14.52MPa,断裂伸长率为518.78%。     

GAP型含能热塑性弹性体的合成及研究进展

概述了含能热塑性弹性体（ETPE）的概念、发展及优势,综述了近年来聚叠氮缩水甘油醚（GAP）型ETPE的合成和研究进展,分析了目前存在的问题和不足,并展望了GAP型ETPE的未来发展趋势及应用前景。     

关于GAP的研究进展

综述了聚叠氮缩水甘油醚(GAP)增塑剂及GAP粘合剂的合成方法,将GAP基粘合剂分类为GAP基热固性含能粘合剂以及GAP基热塑性含能粘合剂,其中GAP基热固性含能粘合剂主要包括了GAP共混改性、支化GAP基热固性含能粘合剂,GAP基热塑性含能粘合剂主要包括了嵌段型GAP基、接枝型GAP基热塑性含能弹性体。对应用更为广泛的GAP基热塑性含能粘合剂的发展趋势和应用前景进行了展望。     

关于GAP的研究进展

综述了聚叠氮缩水甘油醚(GAP)增塑剂及GAP粘合剂的合成方法,将GAP基粘合剂分类为GAP基热固性含能粘合剂以及GAP基热塑性含能粘合剂,其中GAP基热固性含能粘合剂主要包括了GAP共混改性、支化GAP基热固性含能粘合剂,GAP基热塑性含能粘合剂主要包括了嵌段型GAP基、接枝型GAP基热塑性含能弹性体。对应用更为广泛的GAP基热塑性含能粘合剂的发展趋势和应用前景进行了展望。     

叠氮类含能粘合剂研究进展

粘合剂含能化是火炸药未来的发展方向,叠氮类粘合剂是含能粘合剂中的典型代表。该文主要从热塑性含能粘合剂和热固性含能粘合剂两方面综述了近5年叠氮类粘合剂研究进展,并对该类粘合剂的发展趋势和应用前景进行了展望。     

Effect of nitrocellulose (NC) on morphology,rheological and mechanical properties of glycidyl azide polymer based energetic thermoplastic elastomer/NC blends

As a new kind of propellant binder, energetic thermoplastic elastomer (ETPE ) can improve propellant recyclability and environmentally friendly disposal. The rheological behavior of the ETPE binder can be beneficial to identify suitable and safe conditions for processing ETPE propellants. In this paper, ETPE /nitrocellulose (NC ) blends with different mass ratios of NC to ETPE were prepared by the physical mixing method. The heat of explosion and the morphological, thermal, mechanical and rheological properties of the resulting blends were studied systematically. It was found that the heat of explosion of ETPE /NC blends increased with increasing NC content. SEM images showed that the NC domains in the blends changed from tiny pieces to fibers with increasing NC mass ratio, which indicates phase separation in the blends. The tensile mechanical properties of the blends had a peak value when the NC content was 10 wt%, and then increased with the increasing addition of NC . The thermal behavior made clear that the ETPE and NC were partially miscible. Rheological studies on dynamic strain sweep and frequency sweep demonstrated that the content of NC in the blends had a monotonic effect on their rheological properties at 130 °C. Rheological studies also showed that the rheology of the blends is dependent on temperature. The Cole ? Cole and Han plots confirmed phase separation in the blends. © 2016 Society of Chemical Industry     

高能固体推进剂用粘合剂的研究进展

较为系统的从双基推进剂、复合固体推进剂、改性双基推进剂和NEPE推进剂等方面综述了其所用粘合剂的种类及其研究发展概况。介绍了当今新型含能粘合剂的类别和发展状况,并根据目前推进剂的发展要求,指出其粘合剂的发展趋势是含能化的热塑性弹性体。     

Characterization of P(BAMO/AMMO) ETPE Prepared Using Different Diisocyanates

Poly(3,3‐bisazidomethyl oxetane/3‐azidomethyl‐3‐methyl oxetane) energetic thermoplastic elastomers (P(BAMO/AMMO) ETPEs) is one of the most valuable ETPEs in the field of energetic binders. P(BAMO/AMMO) ETPEs were prepared using different diisocyanates (TDI, HMDI, IPDI, and HDI) to investigate the influence of the diisocyanate on the performance of P(BAMO/AMMO) ETPEs. Mechanical properties and heats of formation were investigated. FT‐IR spectroscopy results showed that TDI‐based ETPE has the highest degree of hydrogen bonding with a value of 69.00 %. Mechanical test results showed that the TDI‐based ETPE has better mechanical property with maximum stress at 5.24 MPa and breaking elongation at 390 %. The order for degree of hydrogen bonding and mechanical property of different diisocyanate‐based ETPEs was TDI>HMDI>IPDI>HDI. The heats of formation were calculated by the group additivity method and by the heat of combustion method. The values of heats of formation for TDI‐based ETPE were 3.44 kJ g⁻¹ and 3.75 kJ g⁻¹ according to the two methods. Additionally, TDI‐based ETPE has a lager heat of formation than the other ETPEs.     

Polymer Nanocomposites from Energetic Thermoplastic Elastomers and Alex®

Polymer Nanocomposites (PNs) obtained from linear energetic copolyurethane thermoplastic elastomers (ETPEs) based on GAP and a commercially available nanometric aluminum (Alex) were characterized. Two methods were performed to prepare the PNs: in‐situ and by solvent evaporation. The thermal and mechanical properties of the pure ETPEs, of the composite ETPE/Al (micrometric) and of the nanocomposite ETPE/Alex were studied. The percentage of Alex was adjusted to obtain the optimum mechanical properties. The beneficial effects of the nanopowder on the material properties are highlighted. The introduction of nanoaluminum improves the elasticity and strength of the original ETPE and, consequently, makes it easier to use, to handle, and to process. It indicates that PNs can be considered for future applications in energetic material, such as in gun propellants, rocket propellants and insensitive melt‐cast explosive formulations.     

ETPE发射药的热分解特性与燃烧机理

通过DSC、PDSC分析了点火延迟时间长及难点火ETPE发射药燃烧过程中的热分解特性。用中止燃烧实验装置、SEM电镜观察研究了ETPE发射药燃烧表面的形貌变化及燃烧规律。结果表明,ETPE发射药热分解过程主要由其配方中含能添加剂RDX的热分解过程决定,RDX组分与含能黏结剂BAMO/AMMO聚合物体系之间的燃烧不同步性是造成ETPE发射药点火燃烧性能不佳的主要原因。根据ETPE发射药燃烧过程的特点,归纳出该类发射药的燃烧机理。     

Application of the BAMO‐AMMO Alternative Block Energetic Thermoplastic Elastomer in Composite Propellant

A BAMO‐AMMO alternative block (BAAB)‐based thermoplastic composite propellant with 80 % solid content was prepared using BAAB energetic thermoplastic elastomer (ETPE) as the binder, and the formulation was optimized through energy calculation. The densities, heats of explosion, glass‐transition temperatures, and mechanical properties of the samples were determined by surface tension measurements, oxygen bomb calorimetry, differential scanning calorimetry and static tensile tests, respectively. The results showed that this composite propellant can reach a standard theoretical specific impulse of 275.45 s (10 MPa), a density of 1.8102 g cm⁻³, a heat of explosion of 6256 kJ kg⁻¹, a T_g of −50.46 °C, a tensile strength of 1.56 MPa and an elongation at break of 20 %, thus presenting a superior comprehensive property to BAMO‐AMMO random block (BARB)‐based thermoplastic composite propellant.     

Review on Energetic Thermoplastic Elastomers (ETPEs) for Military Science

Energetic thermoplastic elastomers (ETPE) are futuristic binders for propellant/explosive formulations. Various aspects of ETPEs are addressed in this review. Synthesis modes of different copolymers for ETPEs are discussed. Attention is also given to formulations and thermal studies of ETPE‐based propellants and explosives. Processing methods and parameters of composition are included. As the cost and environmental concerns are prime factors of future generation propellants/explosives, the recovery and reprocessing methods are also briefly discussed.