端环氧聚丁二烯与固体填料之间表界面性能的研究

为了解推进剂中黏合剂与固体填料之间的界面性能,以端环氧聚丁二烯(ETHTPB)为黏合剂,以Al(铝粉)、AP(高氯酸铵)、RDX(黑索金)和HMX(奥克托金)为填料,采用动态接触角测量仪和界面张力仪对黏合剂与固体填料之间的性能(如接触角、表面张力、界面张力、黏附功和铺展系数等)进行了表征和计算。研究结果表明:ETHTPB的表面张力较小,在固体推进剂组分表面易铺展;ETHTPB与固体填料之间的黏附功大小依次为Wa(ETHTPB-AP)Wa(ETHTPB-RDX)Wa(ETHTPB-HMX)Wa(ETHTPB-Al),ETHTPB与固体填料之间的铺展系数大小依次为SSL(ETHTPB-AP)SSL(ETHTPB-RDX)SSL(ETHTPB-HMX)SSL(ETHTPB-Al)。     

含硝胺和铝粉的少烟改性双基推进剂表面和界面性能

研究了不同含氮量的硝化棉(NC)和不同粒度填料(Al、RDX和HMX)的表面性能,NC与填料之间的界面性能,以及表面和界面性能对含硝胺和铝粉的少烟改性双基推进剂力学性能的影响.结果表明,随着RDX、HMX以及A1粉粒度的减小,其表面张力逐渐增大,RDX、HMX与NC之间的界面张力随着RDX和HMX粒度或硝化棉含氮量的减...     

复合固体推进剂用键合剂的研究进展

键合剂是改善黑索金(RDX)、奥克托金(HMX)等硝胺和氧化剂填料与黏合剂间界面作用的关键功能材料,也是提高推进剂力学性能的有效、方便、实用的策略。综述复合推进剂中硼酸酯(BEBA)与中性聚合物(NPBA)等键合剂的研究进展,归纳了键合剂的作用机理,梳理了当前和未来高性能推进剂用键合剂的发展动向,针对不同的黏合剂体系和新的固化方式等发展趋势,设计具有多种功能基团的键合剂结构,积极开发可同时与硝胺、氧化剂及黏合剂相匹配的键合剂,进一步完善补充键合机理,以满足高新武器系统对高力学性能推进剂的需求。     

键合剂对HTPB与Al/Al2O3之间界面作用的分子模拟

采用分子动力学(MD)方法和COMPASS力场,研究了键合剂对丁羟推进剂中端羟基聚丁二烯(HTPB)与Al/Al2O3之间界面的吸附能与力学性能.结果表明,键合剂在Al2O3晶面的吸附能高于HTPB在Al2O3晶面的吸附能,而在Al晶面的规律并不明显.键合剂(TEA)与HTPB在Al2O3晶面吸附能远高于在Al晶面,Al2O3晶体(010)晶面高于 (001)晶面,Al晶体(001)晶面高于(011)晶面.两晶面中吸附能愈高,力学性能愈好.几种键合剂对吸附体系力学性能(弹性模量)的作用次序:TAZ＞TEA＞MAPO·HAC＞MAPO＞HX-752.     

PAN–b–PHEA和PAN–b–P(HEA–g–AEFC)与复合固体推进剂组分的表界面性能

采用动态接触角表面张力仪,研究了PAN–b–PHEA(PAN为聚丙烯腈,HEA为2–羟乙基丙烯酸酯)和PAN–b–P(HEA–g–AEFC)(AEFC为二茂铁甲酸(2–丙烯酰氧乙基)酯)键合剂与不同固体填料(黑索今(RDX)、奥克托今(HMX)、高氯酸铵(AP)、六硝基六氮杂异伍兹烷(CL–20)、Al粉)以及黏合剂体系(端羟基聚丁二烯(HTPB)、星型叠氮缩水甘油醚(S–GAP))间的表界面性能。结果表明:PAN–b–P(HEA–g–AEFC)与配方组分间的黏附功关系为CL–20>HTPB>HMX>RDX>Al粉>S–GAP>AP;PAN–b–PHEA与配方组分间的黏附功关系为CL–20>HTPB>HMX>RDX>Al粉>S–GAP>AP。     

双(二羰基环戊二烯铁)对高氯酸铵热分解性能的影响

采用SEM(扫描电镜)、XPS(X射线光电子能谱)等表征了双(二羰基环戊二烯铁)(简称Fe1)的微观形貌和Fe元素的价态,采用摩擦感度、静电感度和冲击感度测试了Fe1与推进剂相关组分HTPB(端羟基聚丁二烯)、AP(高氯酸铵)、HMX(奥克托今)的安全性能,采用DSC-TG(差热–热重)研究了AP/Fe1及HTPB/Al/AP/HMX/Fe1推进剂的催化热分解性能。结果表明:Fe1的pH为5.79,密度为1.76g/cm~3,其中Fe为零价;Fe1与推进剂相关组分HTPB、AP、HMX的安全性能良好;Fe1催化AP的热分解,AP的转晶峰温提前了2℃,低温分解峰和高温分解峰分别提前了6℃和54℃;在HTPB/Al/AP/HMX推进剂中添加质量分数为5%的Fe1,AP的高温分解峰提前48.1℃;Fe1具有大幅提高HTPB推进剂燃速的潜力。     

AP/Al/SMX/HTPB四组元推进剂能量特性的理论研究

采用推进剂性能评估软件(PEP),计算和比较了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(SMX)和HMX取代高氯酸铵/铝粉/丁羟黏合剂(AP/Al/HTPB)推进剂中AP对配方能量性能的影响。用高温化学平衡计算代码模拟计算了AP/Al/SMX/HTPB和AP/Al/HMX/HTPB复合固体推进剂的能量和标准发动机工作过程。结果表明,与HMX相比,SMX能在更大的配比范围内提高HTPB推进剂的能量水平。在质量分数14%HTPB、18%Al的配方中,SMX能有效将推进剂的平衡流比冲提高到2 622.5N·s/kg,比HTPB三组元能量优化配方高27.5N·s/kg。在质量分数14%HTPB、15%Al的配方中,SMX取代AP后,比冲最高可达2 634.2N·s/kg,比HTPB三组元能量优化配方高39.2N·s/kg。在质量分数15%Al、HTPB质量分数为12%和10%的配方中,SMX质量分数可分别达到45%和65%;最高比冲可分别达到2 652.9和2 679.3N·s/kg,比HTPB三组元能量优化配方分别高57.9和84.3N·s/kg。在不含Al或Al含量很低的配方中,SMX可取代全部AP。     

HMX/AP/Al/HTPB推进剂燃速模拟计算

考察了 HMX/AP/HTPB 推进剂及其组分的热分解特性,当混合氧化剂HMX 和 AP 之质量比为1:1时,其热分解曲线呈现出独特的单峰放热分解特征。考察了十种添加剂对 HMX、AP、HMX/AP 和 HMX/AP/HTPB 热分解性能影响以及对 HMX/AP/Al/HTPB 推进剂燃速的影响。提出了改进的 BDP 模型和燃速模拟计算。     

含团聚硼粉富燃料推进剂一次燃烧模型的建立

为研究团聚硼粉对富燃料推进剂燃烧过程中能量释放和燃速特性的影响,结合实验分析建立了基于BDP模型的含团聚硼粉富燃料推进剂一次燃烧的物理和数学模型.该物理模型中,燃烧表面由团聚硼粉、AP和黏合剂的聚集区两部分组成,气相区形成了AP火焰和FF(终焰)聚集区,团聚硼粉中团聚剂参与了PF(初焰)和FF.在假设团聚硼粉为惰性物质基础上,建立了该推进剂的数学燃烧模型.通过AP/HTPB体系、团聚硼粉/AP/HTPB体系的简化与计算,推导出燃速公式中SAP/S的表达式.该模型充分考虑了团聚硼粉体积分数ζ1对推进剂燃面的影响,将硼粉的体积因素引入含硼富燃料推进剂的数学燃烧模型公式,该模型合理解释了这种推进剂的主要燃烧特性.     

低铝粉含量的HMX/HTPB推进剂研究

对低铝粉含量的HMX/HTPB推进剂进行了配方研究。为获得少烟、高密度、高模量、高燃速、低压强指数的优良的综合性能,配方调试以铝粉质量分数<10%,用HMX替代部分AP来达到少烟目的;以HTPB/TDI/MAPO/STR黏合剂体系来获取高模量;通过AP级配调节,燃速催化剂的选择等方法,使推进剂具有不挥发物质量分数≥88.5%、20℃下密度≥1.78 g/cm3、σm≥3.1 MPa,燃速≥40 mm/s的良好性能,并具有药浆初始黏度低,流动、流平性好的优点。HTPB/AP/Al/HMX四组元推进剂经BSFΦ127标准发动机地面试车,内弹道p–t曲线在压强30 MPa以下,燃烧稳定;推进剂燃烧未急升导致压强异常现象。研制成的药柱经发动机地面试验可知混合比冲高达2 456.7 N·s/kg。     

Effect of Bonding Agent on the Mechanical Properties of GAP High‐Energy Propellant

Three kinds of bonding agent were chosen to improve the mechanical properties of GAP high‐energy composite propellant based on GAP, BuNENA, HMX, AP, and Al. These bonding agents are N,N ′‐bis(2‐hydroxyethyl) dimethylhydantoin and 1,3,5‐trisubstituted isocyanurates (BA1), cyano‐hydroxylated amines (BA2), and hyperbranched polyether with terminal groups substituted by hydroxyl, cyano and ester functional groups (BA3). To study the interaction between bonding agents and oxidizers, the effect of coating by bonding agents on the characteristic absorption peaks of AP and HMX were first studied by infrared spectroscopy. Then the effect of bonding agents on the adhesion work between oxidizers and binder system were determined. The results showed that BA2 has the strongest interaction with AP, whereas BA1 and BA3 have relatively strong interaction with HMX. The AP grain coated by BA2 has the strongest adhesion work to the binder system, and there is not much difference in the values of adhesion work towards binder system of three coated HMX grains. At last the three bonding agents were added to GAP propellant, which has a theoretical specific impulse of 276.03 s. When the three kinds of bonding agent was used alone, the sense of “dewetting” in propellant was relieved but still existed. The combination of BA2 to BA1 or BA3 improved the adhesions between oxidizers and binder system effectively, and the mechanical properties of GAP propellant reached to δ _m=0.69 MPa, ϵ _b=32.7 %.     

Study on the Synthesis and Interfacial Interaction Performance of Novel Dodecylamine‐Based Bonding Agents Used for Composite Solid Propellants

An effective pathway was explored to design and select proper bonding agents that could effectively improve the interfacial interactions between bonding agents and solid particles, with three novel synthesized alkyl bonding agents, dodecylamine‐N,N‐di‐2‐hydroxypropyl‐acetate (DIHPA), dodecylamine‐N,N‐di‐2‐hydroxypropyl‐hydroxy‐acetate (DIHPHA) and dodecylamine‐N,N‐di‐2‐hydroxypropyl‐cyano‐acetate (DIHPCA), as examples. Molecular dynamics simulation was applied to compare unit bond energies of these bonding agents with the [110] crystal face of ammonium perchlorate (AP) and the [120] crystal face of hexogen (RDX). The infrared test was used to characterize the interfacial interactions of these bonding agents with AP or RDX. XPS test was applied to calculate the adhesion percentage of the bonding agents on the surface of precoated AP or RDX particles. All of the above results indicated that these three bonding agents have strong interfacial interactions with AP or RDX in the order of DIHPCA>DIHPHA>DIHPA. The prepared three bonding agents were used in HTPB/AP/RDX/Al propellants, and their effects on tensile strength (σ), elongation under maximum tensile strength (ε_m), elongation at breaking point of the propellant (ε_b) and adhesion index (Φ) of the propellant were studied. The results show that the bonding agents improve the mechanical properties of the propellant in the order of DIHPCA>DIHPHA>DIHPA. The methods found from theoretical design, materials synthesis, and mechanistics studies up to practical application show effective guiding significance for choosing the proper bonding agent and improving the interfacial interactions between the solid particles and binder matrix.     

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.     

含CL-20的NEPE推进剂能量水平分析

用电算法对含有CL－20的NEPE固体推进剂配方的能量特性进行了对分析，并研究了在一这固含量下，配方中不同组分含量对体系能量示性参数的影响，研究结果表明：（1）与含HMX的原基础配方相比，CL－20引入和替代对高能固体推进剂NEPE体系的量能作用具有两重性，即提高能量密度和改善体系氧平衡条件。（2）无论是多铝还是少铝配方，CL－20／Al体系氧平衡值应保在0．52以上，CL－20与Al对体系的能量水平提高具有正加和作用。（3）在高铝含量的原基础配方中，单纯用CL－20替代HMX（体系氧平衡值＞0．51），发动机总得以提高。（4）在低铝含量的基础配方中，用CL－20替代HMX和减少那部分铝后，不仅使得少铝含量（Al≤8％）推进剂体系的能量水平得以显著提高，而且在某种程度上缓解了降低特征信号和提高能量及其他综合性能之间的矛盾。     

Synthesis of Three Novel Laurylamine‐Derived Long‐Chain Alkyl Bonding Agents and Their Interactions with RDX

Three novel long‐chain alkyl bonding agents including 1,1′‐dodecylimino‐bis[3‐[bis(2‐hydroxyethyl)amino]‐2‐propanol (DHAP), 1‐acetyl‐5‐dodecyl‐octahydro‐1,5‐diazocine‐3,7‐diol (ADODD) and 1,3‐bis(dodecylimino)‐5,5‐dimethyl‐2,4‐imidazolidinedione (DDID) were synthesized by modification of laurylamine. Interaction energies between bonding agents and RDX were calculated and compared using the molecular dynamics method. Effects of coating by different bonding agents on characteristic absorption peaks of RDX were analyzed by micro‐infrared spectroscopy. The adhesion degrees of different bonding agents on the surface of RDX solid particles were calculated by XPS methods. The three prepared bonding agents were added to the HTPB/RDX/Al propellant and their effects on σ, ε_m, ε_b and Φ (the adhesion index between filling particles and binder matrix) value of propellant were studied. Simulation and experimental results showed that those three types of long‐chain alkyl bonding agents exhibit a strong interaction with RDX, with highest interaction potencial observed for DHAP, followed by DDID and ADODD. In addition, the current study demonstrated that results obtained by molecular dynamics simulation were in very good agreement with the experimental data.     

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.     

Applying modified hyperbranched polyester in hydroxyl‐terminated polyether/ammonium perchlorate/aluminium/cyclotrimethylenetrinitramine (HTPE/AP/Al/RDX) composite solid propellant

Composite solid propellants demand fine and stable mechanical properties, creep resistance and stress relaxation performance during their long storage and usage time. In this study, modified hyperbranched polyester (MHBPE) was prepared and introduced into HTPE/AP/Al/RDX (HTPE, hydroxyl‐terminated polyether; AP, ammonium perchlorate; RDX, cyclotrimethylenetrinitramine) solid propellant as an effective additive. The static tensile and dynamic mechanical properties of this propellant before and after the introduction of MHBPE were evaluated. The elevated interfacial interaction by using MHBPE between the binder and RDX fillers improved the toughness and elasticity of the propellant. The enhancement mechanisms were also confirmed by the influence on the fracture surface morphology of the binder which was investigated by SEM. In addition, some influence on the dynamic mechanical properties of HTPE/AP/Al/RDX propellant caused by MHBPE was investigated by dynamic mechanical analysis. The creep behaviors of the HTPE/AP/Al/RDX propellants with and without MHBPE were also investigated at different stresses and temperatures. Reduced creep strain rate and strain were obtained for the modified propellant, implying enhanced creep resistance performance. The creep properties were quantitatively evaluated using a six‐element model and the long‐term creep performance of the propellant was predicted using the time–temperature superposition principle. A creep behavior of nearly 10⁶ s at 30 °C could be acquired in a short‐term experiment (800 s) at 30–70 °C. Moreover, the stress relaxation investigation of the propellants with and without MHBPE at ?40 °C, 20 °C and 70 °C suggested that MHBPE/HTPE/AP/Al/RDX propellant possessed better response ability to deformation. Thus, the application of MHBPE provides an efficient route of reinforcement to enhance the creep resistance and stress relaxation properties. © 2020 Society of Chemical Industry     

The Mechanism of Filler Reinforcement from addition of neutral polymeric bonding agents to energetic polar propellants

It has been demonstrated that addition of small amounts of the newly developed neutral polymeric bonding agents (NPBA's) to energetic propellants such as HMX/PEG/NG composites causes strong filler reinforcement. The mechanism of this reinforcement occurs through interfacial effects, and not because of an overall increase in the crosslink density of the binder. It has been demonstrated directly that the NPBA's have a favorable relative affinity for HMX and concentrate at the solid surface during mixing. All the experimental evidence supports the theory that highly crosslinked polymeric shells form around the HMX particles and chemically bond to the binder matrix during the cure, thus causing an increase in the initial modulus. Furthermore, these shells appear to eliminate the weak, soft layers around the particles, and hence filler reinforcement persists up to much higher elongation than without addition of NPBA. Based on the filler reinforcement observed, the simple one-step procedure of incorporating our NPBA is almost as effective as the more costly process of precoating the particles.     

Aging of ADN Rocket Propellant Formulations with Desmophen®‐Based Elastomer Binder

Desmophen® binder‐based rocket propellant formulations containing ammonium dinitramide (ADN) and different fuel filler types (Al, HMX) were manufactured and investigated. Desmophen® D2220 is a polyesterpolyol. Polyesters are seen as a binder possibility, because of the relatively low temperature of the glass transition region compared to polyether‐based prepolymers such as GAP. The analogous formulations with AP instead of ADN were also included for comparison. The aging was followed by SEM, DSC, and DMA measurements. The accelerated aging program was developed on the principle of thermal equivalent load and the generalized van’t Hoff rule with a scaling factor equal to F=2.9. The aging was performed in air (RH<10 %) at temperature values between 65 and 85 °C and aging times adjusted to a thermal equivalent load of 15 years at 25 °C. DMA measurements of the aged ADN/Desmophen®‐based propellants identified changes in the loss factor curve. In contrast to HTPB‐Al‐AP rocket propellant formulations, the loss factor curve of the ADN formulations with Desmophen®‐based elastomer binder shows only one main apparent peak. The loss factor curves were modeled with exponentially modified Gaussian functions, which have revealed the presence of a second hidden peak. It was found that the aging could be characterized by the time‐temperature dependence of the areas of the hidden peak. The area increased with aging, which is explained by scissioning of the polymer in the shell around the ADN particles. By this process the strength is reduced, which was recognized by the decrease in storage shear modulus.