AP assembled on ultrafine aluminum particle and its application to NEPE propellant

Coating modification is an important way to enhance the reactivity of aluminum powder.In this paper,ammonium perchlorate and aluminum powder were assembled into energetic microunits by liquid deposition method.Spherical particles with AP as shell and ultrafine aluminum powder as the core(Al@AP)were gained.The micromorphology results show that the coated particles are about 5μm,and the coating layer is evenly distributed on the outer surface of aluminum powder,indicating a complete coating.The energetic microunits were implanted into the nitrate ester plasticizing adhesive system(NEPE)as solid phase fillers.The effect of filler on the rheological properties,safety,mechanical properties,thermal reaction and energy properties of the system was analyzed by comparing with the raw aluminum filler.The test results show that the rheological properties,mechanical properties and pressure index of NEPE containing system Al@AP meets the requirements of solid propellant charging.Compared with Al based propellant,the mechanical sensitivity and thermal sensitivity are decreased,the safety is better,and the explosion heat of the propellant is increased by 7.8%.The engine test shows that the specific impulse is increased by 1.2 s.Al@AP can improve the energy output and safety of NEPE propellant,and has potential application prospects in high-energy propellants.

Investigations of the mechanical response of dummy HTPB propellant grain under ultrahigh acceleration overload conditions using onboard flight-test measurements

In this paper,to study the mechanical responses of a solid propellant subjected to ultrahigh acceleration overload during the gun-launch process,specifically designed projectile flight tests with an onboard measurement system were performed.Two projectiles containing dummy HTPB propellant grains were successfully recovered after the flight tests with an ultrahigh acceleration overload value of 8100 g.The onboard-measured time-resolved axial displacement,contact stress and overload values were successfully obtained and analysed.Uniaxial compression tests of the dummy HTPB propellant used in the gunlaunched tests were carried out at low and intermediate strain rates to characterize the propellant's dynamic properties.A linear viscoelastic constitutive model was employed and applied in finite-element simulations of the projectile-launching process.During the launch process,the dummy propellant grain exhibited large deformation due to the high acceleration overload,possibly leading to friction between the motor case and propellant grain.The calculated contact stress showed good agreement with the experimental results,though discrepancies in the overall displacement of the dummy propellant grain were observed.The dynamic mechanical response process of the dummy propellant grain was analysed in detail.The results can be used to estimate the structural integrity of the analysed dummy propellant grain during the gun-launch process.

Estimation of surface geometry on combustion characteristics of AP/HTPB propellant under rapid depressurization

The 2D sandwich model serves as a potent tool in exploring the influence of surface geometry on the combustion attributes of Ammonium perchlorate/Hydroxyl-terminated polybutadiene(AP/HTPB)propellant under rapid pressure decay.The thickness of the sandwich propellant is derived from slicing the 3D random particle packing,an approach that enables a more effective examination of the micro-flame structure.Comparative analysis of the predicted burning characteristics has been performed with experimental studies.The findings demonstrate a reasonable agreement,thereby validating the precision and soundness of the model.Based on the typical rapid depressurization environment of solid rocket motor(initial combustion pressure is 3 MPa and the maximum depressurization rate is 1000 MPa/s).A-type(a flatter surface),B-type(AP recesses from the combustion surface),and C-type(AP protrudes from the combustion surface)propellant combustion processes are numerically simulated.Upon comparison of the evolution of gas-phase flame between 0.1 and 1 ms,it is discerned that the flame strength and form created by the three sandwich models differ significantly at the beginning stage of depressurization,with the flame structures gradually becoming harmonized over time.Conclusions are drawn by comparison extinction times:the surface geometry plays a pivotal role in the combustion process,with AP protrusion favoring combustion the most.

The regulation of ferrocene-based catalysts on heat transfer in highpressure combustion of ammonium perchlorate/hydroxyl-terminated polybutadiene/aluminum composite propellants

The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.

Synthesis of multifunctional additives for solid propellants:Structure,properties and mechanism

To simplify the composite propellant formulation and address the current issue of the single-functionality present in existing additives,the multi-cyano,amine-based polybutadiene(AEHTPB-CN)was prepared based on AEHTPB by adopting appropriate synthesis strategies.By replacing 10% of HTPB binder in the propellant formulation,it can effectively enhance the interfacial bond strength between the propellant binder matrix and solid fillers(AP(ammonium perchlorate)and RDX(cyclotrimethylene-trinitramine)),the mechanical properties of the HTPB/AP/RDX/Al propellant were superior to blank control propellant with an improvement of 35.4% in tensile strength,62.0% enhancement in elongation at break,and reduce the propellant burn rate by 10.7% with any energy loss.The function mechanism of AEHTPB-CN was systematically elucidated through experiments and computer simulation techniques.The results show that the tertiary amine group in AEHTPB-CN can react with AP to form ammonium ionic bonds,and the hydroxyl and cyano groups can form hydrogen bonding interactions with AP,which enables AEHTPB-CN to be firmly adsorbed on the AP surface through chemical and physical interactions.For RDX,the interfacial bonding effect of AEHTPB-CN is attributed to their ability to form C-H···N≡C weak hydrogen bonding interaction between the cyano group and RDX methylene group.

Investigation of high rate mechanical flow followed by ignition for high-energy propellant under dynamic extrusion loading

Investigating the ignition response of nitrate ester plasticized polyether(NEPE) propellant under dynamic extrusion loading is of great significant at least for two cases. Firstly, it helps to understand the mechanism and conditions of unwanted ignition inside charged propellant under accident stimulus.Secondly, evaluates the risk of a shell crevice in a solid rocket motor(SRM) under a falling or overturning scene. In the present study, an innovative visual crevice extrusion experiment is designed using a dropweight apparatus. The dynamic responses of NEPE propellant during extrusion loading, including compaction and compression, rapid shear flow into the crevice, stress concentration, and ignition reaction, have been firstly observed using a high-performance high-speed camera. The ignition reaction is observed in the triangular region of the NEPE propellant sample above the crevice when the drop weight velocity was 1.90 m/s. Based on the user material subroutine interface UMAT provided by finite element software LS-DYNA, a viscoelastic-plastic model and dual ignition criterion related to plastic shear dissipation are developed and applied to the local ignition response analysis under crevice extrusion conditions. The stress concentration occurs in the crevice location of the propellant sample, the shear stress is relatively large, the effective plastic work is relatively large, and the ignition reaction is easy to occur. When the sample thickness decreases from 5 mm to 2.5 mm, the shear stress increases from 22.3 MPa to 28.6 MPa, the critical value of effective plastic work required for ignition is shortened from 1280 μs to 730 μs, and the triangular area is easily triggering an ignition reaction. The propellant sample with a small thickness is more likely to stress concentration, resulting in large shear stress and effective work, triggering an ignition reaction.

Experimental study on thermal decomposition kinetics of natural ageing AP/HTPB base bleed composite propellant

The kinetics of the thermal decomposition for a naturally ageing ammonium perchlorate(AP) and hydroxyl-terminated-polybutadiene(HTPB) base bleed composite propellant were investigated using a differential scanning calorimetry(DSC). The naturally ageing AP/HTPB base bleed propellant samples have been stored in a sealed plastic bag at room temperature(5-25 ℃) for more than 20 years. The experimental DSC results were obtained by placing samples(each about 1.5 mg) in a sealed pan under non-isothermal condition under different heating rates, 5.0, 10.0, 15.0, 20.0 and 30.0 ℃·min^(-1). The activation energy and pre-exponential factor were estimated based on the relationship between the exothermic peak temperature and the heating rate by Ozawa and Kissinger methods, respectively. The decomposition kinetic parameters is lower the values under laboratorial aging condition.

Research on the influences of confining pressure and strain rate on NEPE propellant:Experimental assessment and constitutive model

In order to study the influences of confining pressure and strain rate on the mechanical properties of the Nitrate Ester Plasticized Polyether(NEPE)propellant,uniaxial tensile tests were conducted using the selfmade confining pressure system and material testing machine.The stress-strain responses of the NEPE propellant under different confining pressure conditions and strain rates were obtained and analyzed.The results show that confining pressure and strain rate have a remarkably influence on the mechanical responses of the NEPE propellant.As confining pressure increases(from 0 to 5.4 MPa),the maximum tensile stress and ultimate strain increase gradually.With the coupled effects of confining pressure and strain rate,the value of the maximum tensile stress and ultimate strain at 5.4 MPa and 0.0667 s^(-1)is 2.03 times and 2.19 times of their values under 0 MPa and 0.00333 s^(-1),respectively.Afterwards,the influence mechanism of confining pressure on the NEPE propellant was analyzed.Finally,based on the viscoelastic theory and continuous damage theory,a nonlinear constitutive model considering confining pressure and strain rate was developed.The damage was considered to be rate-dependent and pressuredependent.The constitutive model was validated by comparing experimental data with predictions of the constitutive model.The whole maximum stress errors of the model predictions are lower than 4%and the corresponding strain errors are lower than 7%.The results show that confining pressure can suppress the damage initiation and evolution of the NEPE propellant and the nonlinear constitutive model can describe the mechanical responses of the NEPE propellant under various confining pressure conditions and strain rates.This research can lay a theoretical foundation for analyzing the structural integrity of propellant grain accurately under working pressure loading.

Molecular simulation study of the stabilization process of NEPE propellant

In this reported study, the density functional theory(DFT) was used at the(U)B3LYP/6-311G(d,p) level to investigate the stabilization process of the nitrate ester plasticized polyether propellant(NEPE). Molecular simulations were conducted of the reaction that generates NO_(2), the autocatalytic and aging reaction triggered by the NO_(2), and the nitrogen dioxide absorption reaction of the stabilizers during the propellent stabilization process. These simulations were derived using the transition-state theory(TST)and variational transition-state theory(VTST). The simulation results suggested that the stabilization of the NEPE propellant consisted of three stages. First, heat and NO_(2) were generated during the denitrification reaction of nitroglycerine(NG) and 1,2,4-butanetriol trinitrate(BTTN) in the NEPE propellant.Second, nitroso products were generated by the reactions of N-Methyl-4-nitroaniline(MNA) and 2-nitrodiphenylamine(2NDPA) with NO_(2). Third, the stabilizers were exhausted and the autocatalytic reaction of NG and BTTN and the aging reaction of polyethylene glycol(PEG) were triggered by the heat and NO_(2)generated in the first stage. By comparing the energy barriers of the various reactions, it was found that the NO_(2)generated from the denitrification reaction significantly reduced the reaction energy barrier to 105.56-126.32 kJ/mol, also increased the reaction rate constant, and decreased the thermal stability and energetic properties of the NEPE propellant. In addition, the NO_(2)also weakened the mechanical properties of the NEPE propellant by attacking the-CH2groups and the O atoms in the PEG molecular chain. The energy barriers of the reactions of MNA and 2NDPA with NO_(2)(94.61-133.61 k J/mol) were lower than those of the autocatalytic and decomposition reactions of NG, BTTN, and the aging reactions of PEG(160.30-279.46 kJ/mol). This indicated that, by eliminating NO_(2), the stabilizer in the NEPE propellant can effectively prevent NO_(2)from reacting with the NG, BTTN, and PEG in the NEPE propellant. Consequently, this would help maintain the energy and mechanical properties of the NEPE propellant, thereby improving its thermal stability.

Effects of Plasticizers,Antioxidants and Burning Rate Modifiers on Aging Performance of the HTPB/HMDI Composite Solid Propellant

The effects of plasticizers,antioxidants and burning rate modifiers on the aging performance of the composite solid propellant based on hydroxyl-terminated polybutadiene(HTPB)/hexamethylene diisocyanate(HMDI)were explored by apply-ing an accelerated aging program for 90 day at 70 ℃. The HTPB propellant matrix with the diisooctyl sebacate(DOS)as plasti-cizers and diisooctyl azelate(DOZ), antioxidants as N,N ′-Diphenyl-p-phenylenediamine(AO) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol)(cyanox 2246)and burning rate modifiers as barium ferrite(BF),copper chromites(CC)and fer-ric oxide(FO)were varied. Results show that sample(S1)which based on DOS decreases the stress value and increases the strain value which considered to be an excellent start for aging program. Sample(S3)containing AO presents the higher resis-tance to oxidation showing the better performance that reflects on increasing the shelf life of the composite solid propellant mo-tor. Sample(S5)which based on BF enhances the ballistic performance among over the other tested two samples. The accelerat-ed aging program allowed us to estimate the motor in-service lifetime.

The Influence of Aziridine on the Aging of Composite Solid Rocket Propellant

Aging of a solid composite propellant containing HTPB/AP/AL was performed in order to validate the conformance of the accelerated aging data to the Arrhenius law. The main objective of the work was to examine the influence of the aziridine bonding agents family on the propellant aging. Aging of the prepared propellant samples was conducted as follows: 1. Four samples, one free of bonding agents, and three containing aziridine based bonding agents MAPO,HX-752, MAT4 were aged at 65°C. 2. Another four samples based on HX-752, MAT4 with different curing agents were aged at 65°C. The measured mechanical properties of the free bonding agent propellant samples were very far from the specifications and this illustrates the importance of the bonding agents in both the preparation and the aging phases.The prepared bonding agent 'MAT4' gave remarkable improvements of the mechanical properties comparing with HX-752 and MAPO. The aziridine bonding agents family inhibited the rate of decomposition of the propellant during the aging periods and supported the propellant matrix against decomposition at the elevate temperatures. Using of HMDI as curing agent gave slight better mechanical properties to the IPDI.

HTPB／TDI衬层与NEPE推进剂的界面反应机理

采用富立叶变换红外光谱(FTIR)和全反射红外光谱(FTIR/ATR),研究了半固化的HTPB/TDI衬层表面的活性基团以及不同的—NCO基团与不同羟基的反应速率。结果表明,半固化的HTPB/TDI衬层表面含有大量的—NCO基团;HTPB/TDI衬层和NEPE推进剂粘合剂相的—NCO基与—OH的交叉反应速度较NEPE推进剂的固化反应速度快得多。HTPB/TDI衬层与NEPE推进剂界面的化学反应机理是粘合剂相中—OH基和—NCO基的交叉反应,其中衬层中TDI分子的—NCO基与PEG分子的—OH基的反应速度稍快于NEPE推进剂中N100分子的—NCO基与HTPB分子的—OH基的反应;在界面区域,HTPB/TDI衬层与NEPE推进剂通过氨基甲酸酯键形成化学粘接。

NEPE推进剂用HTPB衬层老化研究(Ⅰ)——化学环境对衬层老化行为的影响

根据衬层的使用特点,研究了NEPE推进剂用HTPB衬层在NEPE推进剂环境及自由状态下的老化特性,发现NEPE推进剂对HTPB衬层的固化和老化都有严重影响。NEPE推进剂药浆影响HTPB衬层固化,导致衬层固化不完全。NEPE推进剂环境下的取样衬层与衬层材料具有不同的老化机理。取样衬层老化过程中HTPB网络发生了交联反应,模量、凝胶分数增大;而衬层材料老化以降解断链反应为主。老化对衬层材料动态损耗因子没有明显影响,但对取样衬层损耗因子曲线α峰影响显著。

NEPE推进剂用HTPB衬层老化研究(Ⅱ)——化学参量表征老化效应的应力松弛模型

为了研究NEPE推进剂环境下HTPB衬层老化对松弛模量的影响,从75℃老化不同时间的NEPE推进剂/HTPB衬层粘接试件中取得衬层试样,进行了不同温度下衬层的拉伸应力松弛测试,并获得了相应的凝胶分数测试数据。根据时-温等效原理将不同老化时间的衬层的松弛模量数据制作成松弛模量主曲线,并分别用Prony级数进行拟合。结果显示,老化对松弛模量的弹性部分有显著影响,对粘性部分影响很小。忽略老化对粘性部分的影响,建立了含老化效应的衬层应力松弛模型。建立了修正的弹性模量-凝胶分数关系模型,并根据衬层实验数据验证了该模型。结合上述2个模型,得到了化学参量表征老化效应的衬层应力松弛模型。对该模型的应用进行了讨论,发现外推至常温,应力松弛与老化在不同的时间尺度起作用,松弛模量可用分段函数描述。

长期贮存发动机中HTPB推进剂老化特性及蠕变本构模型

为了研究固体火箭发动机长期贮存期间老化对推进剂力学性能的影响,开展了三种温度(50℃,60℃与70℃)下为期60天的高温加速老化试验。对老化前后HTPB推进剂进行了定速拉伸试验与蠕变试验,并采用扫描电镜观察了其表面细观形貌。引入扩裂元件,结合Arrhenius方程,建立了含老化因子的推进剂蠕变全过程本构模型,利用试验数据拟合了模型参数并验证了其有效性。结果表明:随着老化进程的加剧,推进剂最大伸长率逐渐减小,最大抗拉强度会依次出现下降、波动、上升三个阶段。所建本构模型能较好地表征贮存1.5年后推进剂的蠕变全过程,预测曲线与试验结果曲线最大误差为13.35%。

低应变率下NEPE推进剂“双屈服”特性及其粘-弹-塑性屈服模型

固体发动机全寿命周期中,推进剂药柱长期处于低应变率状态。为了分析硝酸酯增塑聚醚(NEPE)推进剂在低应变率下的屈服与损伤特性,开展了NEPE推进剂在低应变率(1.190×10^(-5)~2.381×10^(-2)s^(-1))下的单轴拉伸试验。研究表明,NEPE推进剂的应力-应变曲线呈“双屈服”态,最大抗拉强度、断裂强度随拉伸速率的下降而明显下降,但初始屈服点(“脱湿点”)与后继屈服点不受应变率的影响,两级屈服点应变近似保持一个稳定值,分别为13.5%和55.4%。因此,可将“脱湿点”应力视为推进剂的屈服强度。在此基础上,构建了NEPE推进剂粘-弹-塑性屈服模型,通过引入动屈服函数,建立了动屈服强度、粘塑性应变率与静屈服强度之间的关系。结合试验数据,NEPE推进剂静屈服强度为0.22 MPa。

HTPB推进剂热力耦合加速老化细观损伤机理分析

为了深入探究端羟基聚丁二烯(HTPB)推进剂在热力耦合作用下的细观损伤机理,采用了试验表征和理论分析相结合的方法。具体而言,对在不同环境温度(50,70℃和90℃)及不同加载次数下的HTPB推进剂进行了细观层面分析。在50℃下,分别进行了约3000次和10800次加载;在70℃下,分别进行了约1800,3600次和7030次加载;而在90℃下,则进行了约1800次加载。研究发现:在热力耦合加速老化作用下,HTPB推进剂的细观损伤比单一因素老化更为显著。其细观损伤机理主要涉及两方面:一是由于基体热降解,基体自身的承载性能及其与颗粒间的粘接强度均有所下降,进而导致颗粒“脱湿”;二是颗粒的“脱湿”现象反过来进一步加剧了基体的热降解。这种相互作用使得细观损伤更加严重。研究还发现,随着老化温度的增加,细观损伤的程度会加剧,但温度过高将改变老化过程的细观损伤机理。此外,研究指出,在其他条件不变的前提下,合理选择终止加载次数对于判断HTPB推进剂是否发生显著细观损伤至关重要。本研究中,当50℃和70℃下的加载次数比(N/N_(End))分别超过0.281和0.330时,HTPB推进剂会产生显著的细观损伤。

NEPE推进剂/衬层界面固化反应机理的理论研究

推进剂/衬层界面是固体火箭发动机燃烧室中的关键结构。采用密度泛函理论(DFT)研究了硝酸酯增塑聚醚(NEPE)推进剂/衬层粘合界面的反应机理,评估了界面结构中不同组分之间的反应途径和过渡态结构,包括聚乙二醇(PEG)、甘油(GO)、三乙醇胺(TEA)、N,N,N′,N′-四(2-羟乙基)乙二胺(THEED)、甲苯二异氰酸酯(TDI)、异佛尔酮二氰酸酯(IPDI)和多官能度异氰酸酯(N-100);得到不同组分间反应路径的吉布斯自由能曲线。结果表明,TDI与PEG、GO、TEA和THEED之间的反应竞争性发生在第二步修饰反应,即第二个—NCO基团与端羟基的氢转移反应生成产物——聚氨酯;含羟基化合物中端羟基的增多有利于与2,4-TDI反应,但对2,6-TDI体系影响不大。此外,对比相关基元反应决速步的反应速率常数可知,2,4-TDI体系的反应速率常数大多高于2,6-TDI体系、IPDI体系和N-100体系,基元反应PEG+INT1较易发生,而基团反应N-100/THEED最慢发生。

基于随机本构模型的HTPB推进剂装药结构完整性评估

针对HTPB推进剂力学性能的分散性问题,引入用对数正态概率密度函数描述的随机参数,构建随机本构模型,开展了基于随机本构模型的发动机药柱在点火增压工况下的结构完整性分析。结果表明:通过随机本构模型预测的5组应力应变曲线与试验的5组应力应变曲线重合度较高,试验曲线全部落在95%的概率区间之内,随机本构模型可以较好地反映推进剂材料的分散性;药柱的力学响应与随机参数有关,最大Von Mises应力、最大Von Mises应变、最大位移、最大损伤指数及安全系数均与随机参数呈近似线性关系;基于试验曲线拟合的本构模型和基于概率区间预测的随机本构模型获得的药柱力学响应误差不超过1%,基于概率区间预测的随机本构模型可以准确预测点火增压载荷下的药柱力学响应。

应变率对高固含量HTPB推进剂力学特性与破坏机制的影响

通过不同拉伸速率下的单轴拉伸力学性能试验,研究了应变率与90%固含量(固体颗粒的质量分数)HTPB推进剂力学性能之间的相关性,并采用扫描电镜对拉伸断面进行了观察,分析了应变率对推进剂力学性能和破坏机制的影响。结果表明,在低应变率条件下,推进剂的应力—应变曲线出现了弧段现象;随着应变率增加,推进剂应力—应变曲线逐渐由5段式变为4段式;推进剂的初始模量、最大抗拉强度随应变率的增大呈现出上升趋势;推进剂的最大延伸率随应变率增大呈现出降低趋势,在应变率为1190.48×10^(-4)s^(-1)时最大延伸率仅为33.9%;随着应变率增大,高固含量HTPB推进剂的破坏机制逐渐由颗粒“脱湿”转变为基体撕裂,无颗粒破碎产生。