Combustion Properties of Metal Particles as Components of Modified Double-Base Propellants

Metal particles such as aluminum（ Al）,magnesium（ Mg）,boron（ B） and nickel（ Ni）,as well as Mg/Al alloy（ Mg/Al = 3/4） are currently the most widely used ingredients in modified doublebase propellants. In this contribution,the combustion properties of the metal species are studied by means of the high-speed photography technique and the non-contact wavelet-based measurement of flame temperature distribution. The combustion process of the Al,Mg and Mg/Al samples shows both gas phase reaction and surface oxidation,which yield volatile and nonvolatile products,corresponding to the oxide and suboxide respectively. However,the combustion of B and Ni shows only gas phase reaction,due to their high melting point as well as high enthalpy of vaporization. In addition to the experiments,a hypothetical combustion model has been proposed to clarify the combustion characteristics of metal species in modified double-base propellants.

Novel aspects for thermal stability studies and shelf life assessment of modified double-base propellants

Modified DB propellants, based on energetic nitramine(RDX) were manufactured by solventless extrusion process. Thermal stability and shelf life assessment of modified DB propellant were investigated. Shelf life assessment was evaluated using Van’t Hoff’s formula and artificial aging at 70℃ up to120 days. Quantification of total heat released and heat flow with aging time was conducted using differential scanning calorimetry(DSC) and thermal activity monitoring(TAMIII) respectively. Modified DB formulation based on 20 wt % RDX demonstrated enhanced thermal stability in terms of controlled heat flow, and slow decomposition reactions at elevated temperature. This formulation demonstrated extended service life up to 56 years compared with reference formulation. These novel finding was ascribed to the high thermal stability of RDX and its compatibility with DB constituents. This manuscript shaded the light on novel and effective approach for thermal stability via monitoring thermal activity with aging.

Novel approach to quantify the chemical stability and shelf life of modified double-base propellants

Double-base(DB) propellant is vulnerable to auto-catalytic decomposition reactions during storing with the evolution of nitrogen oxides. Modified DB propellant based on energetic nitramines(RDX) can offer enhanced thrust and action time. This study is devoted to evaluate the impact of RDX on chemical stability and shelf life of DB propellant. Extruded modified DB propellant based on RDX was manufactured by solventless extrusion process. Shelf life assessment was performed using an artificial aging at70 ℃ up to 120 days and employing Van't Hoffs formula. Quantification of evolved NOx gases and stabilizer depletion with aging time was conducted using Bergmann-Junk test and HPLC respectively.Modified DB formulation based on RDX 20 wt % demonstrated enhanced chemical stability and extended service life up to 46 years compared with reference formulation. This finding was ascribed to the high chemical and thermal stability of RDX as well as its compatibility with DB constituents; no side chemical reactions could take place during storing. This manuscript shaded the light on RDX as effective energetic constituent that offered DB propellants with enhanced performance, good chemical stability, and extended service life.

Simulation of the plasticizing behavior of composite modified doublebase(CMDB)propellant in grooved calendar based on adaptive grid technology

The frequent occurrence of safety accidents during the calendering process is caused by the flammable and explosive properties of composite modified double-base(CMDB)propellant.Optimization of process parameters with the aid of fluid simulation technology could effectively ensure the safety of the calendering process.To improve the accuracy of the simulation results,material parameters and model structure were corrected based on actual conditions,and adaptive grid technology was applied in the local mesh refinement.In addition,the rheological behavior,motion trajectories and heat transfer mechanisms of CMDB propellant slurry were studied with different gaps,rotational rates and temperatures of two rollers.The results indicated that the refined mesh could significantly improve the contour clarity of boundaries and simulate the characteristics of CMDB propellant slurry reflux movement caused by the convergent flow near the outlet.Compared with the gap,the increased rotational rate of roller could promote the reflux movement and intensify the shear flow of slurry inside the flow region by viscous shear dragging.Meanwhile,under the synergistic effect of contact heat transfer as well as convective heat exchange,heat accumulated near the outlet and diffused along the reflux movement,which led to the countercurrent heat dissipation behavior of CMDB propellant slurry.The plasticizing mechanism of slurry and the safety of calendering under different conditions were explored,which provided theoretical guidance and reference data for the optimization of calendering process conditions.Based on the simulation results,the safety of the CMDB propellant calendering process could be significantly improved with a few tests conducted during a short research and development cycle.

A Study of Estimating the Safe Storage Life, Self-accelerating Decomposition Temperature and Critical Temperature of Thermal Explosion of Double-base Propellant Using Isothermal and Non-isothermal Decomposition Behaviours

A method of estimating the safe storage life （τ）, self-accelerating decomposition temperature （TsADT） and critical temperature of thermal explosion （Tb） of double-base propellant using isothermal and non-isothermal decomposition behaviours is presented. For double-base propellant composed of 56±1wt% of nitrocellulose （NC）, 27±0.5wt% of nitroglycerine （NG）, 8.15±0.15wt% of dinitrotoluene （DNT）, 2.5±0.1wt% of methyl centralite, 5.0±0.15wt% of catalyst and 1.0±0.1wt% of other, the values of r of 49.4 years at 40℃, of TSAOT of 151.35℃ and of Tb of 163.01℃ were obtained.

Study on Influence of Functional Composition Distribution on Combustion Performance of a Modified Single Base Propellant

The modified single base propellant samples were prepared by impregnating blasting oil into single base grains and deactivating deterrent in water medium. The concentration distribution of functional compositions in this propellant was determined by using FTIR micro-spectroscopy. Its combustion performance was investigated by means of closed-bomb and interior ballistic tests. The results show that the concentration of NG distributes parabolically along the radius and the concentration of NA decreases from the surface to the centre exponentially. The deeper the NG impregnates, the slower the NA concentration decreases, the stronger the progressive combustion is and the better the interior ballistic performance is. When the depth corresponding to maximum NG concentration is about 1/2 of the web and the NA decreases slowly, the progressive combustion is the strongest and the interior ballistic performance is the best.

Damage-ignition mechanism studies on modified propellant with different crosslinking density under dynamic loading

The study of high-energy and low-vulnerability propellants is important for the power performance and safety of solid propellant rocket motors.The modified split Hopkinson pressure bar(SHPB)tests are performed on two kinds of propellant with different crosslinking density to study the dynamic mechanical responses and damage-ignition mechanism.SHPB apparatus is equipped with a highperformance infrared camera and high-speed camera to capture the deformation,damage-ignition feature and temperature evolution images in the impact process.The results suggested that the mechanical responses and damage-ignition mechanism of the propellants were affected by the strain rates and crosslinking density.The damage-ignition degree is more intense and the reaction occurs earlier with the increase of strain rates.For propellant 1 with higher crosslinking density,the critical ignition strain rate is 4500 s^(-1).Two kinds of propellants show different ignition mechanism,i.e.crack generation,propagation and final fracture for propellant 1 while viscous shear flow for propellant 2.Meanwhile,the SEM images also reveal the difference of damage-ignition mechanism of the two kinds of propellants.Finally,the ignition mechanism under different strain rates and critical ignition strain rate of propellants are further explained by the theoretical calculation of temperature variations.

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.

Recent advances in catalytic combustion of AP-based composite solid propellants

Composite solid propellants(CSPs) have widely been used as main energy source for propelling the rockets in both space and military applications. Internal ballistic parameters of rockets like characteristic exhaust velocity, specific impulse, thrust, burning rate etc., are measured to assess and control the performance of rocket motors. The burn rate of solid propellants has been considered as most vital parameter for design of solid rocket motors to meet specific mission requirements. The burning rate of solid propellants can be tailored by using different constituents, extent of oxidizer loading and its particle size and more commonly by incorporating suitable combustion catalysts. Various metal oxides(MOs),complexes, metal powders and metal alloys have shown positive catalytic behaviour during the combustion of CSPs. These are usually solid-state catalysts that play multiple roles in combustion of CSPs such as reduction in activation energy, enhancement of rate of reaction, modification of sequences in reaction-phase, influence on condensed-phase combustion and participation in combustion process in gas-phase reactions. The application of nanoscale catalysts in CSPs has increased considerably in recent past due to their superior catalytic properties as compared to their bulk-sized counterparts. A large surface-to-volume ratio and quantum size effect of nanocatalysts are considered to be plausible reasons for improving the combustion characteristics of propellants. Several efforts have been made to produce nanoscale combustion catalysts for advanced propellant formulations to improve their energetics. The work done so far is largely scattered. In this review, an effort has been made to introduce various combustion catalysts having at least a metallic entity. Recent developments of nanoscale combustion catalysts with their specific merits are discussed. The combustion chemistry of a typical CSP is briefly discussed for providing a better understanding on role of combustion catalysts in burning rate enhancement. Available information on different types of combustion nanocatalysts is also presented with critical comments.

Thermal kinetic and thermal safety of Shuangfang-3 gun propellant based on thermal decomposition characteristics

Differential scanning calorimetry(DSC)was used to investigate the thermal decomposition and thermal safety characteristics of Shuangfang-3(SF-3)gun propellant.The kinetic calculation of the DSC curve was carried out by Kissinger and Friedman models,and the time to the maximum rate under adiabatic conditions and the self-accelerating decomposition temperature were calculated by using the AKTS thermal analysis software in combination with the heat balance equation.The thermal history experiment was carried out to further analyze the autocatalytic properties of SF-3.The results show that the initial decomposition temperature,decomposition peak temperature,and decomposition completion temperature of SF-3 all move to the high temperature direction with the increase of heating rate,and the average decomposition heat is 1521.4 J/g.The kinetic model showcased that SF-3 has different reactions in different reaction stages,and its apparent activation energy is 168.2 kJ/mol.When the times to maximum rate under adiabatic conditions are 2.0 h,4.0 h,8.0 h,24.0 h,respectively,the corresponding temperatures are 130.7℃,124.8℃,119.2℃and 110.5℃,respectively.When the masses are 5.0 kg,15.0 kg,25.0 kg,50.0 kg,100.0 kg,respectively,the corresponding self-accelerating decomposition temperatures are 110.0℃,105.0℃,102.0℃,99.0℃and 96.0℃,respectively.As the packaging mass increases,it is more difficult to exchange the liberated heat into the surrounding environment and its safety would be further reduced.The thermal history experiment demonstrates that the thermal decomposition of SF-3 is an n-stage reaction and does not have autocatalytic properties.Therefore,the size and ventilation conditions of the sample have a certain impact on the storage stability of SF-3.In the actual production,usage,storage and transportation,sample size and ventilation conditions should be controlled,and practical and effective measures should be taken according to the actual situation.

甲基紫试验中改性双基推进剂的热分解机制研究

目的 研究甲基紫试验中含Al改性双基推进剂以及含RDX改性双基推进剂2种典型改性双基推进剂的热分解机理。方法 将这2种典型改性双基推进剂与普通双基推进剂进行对比试验,采用TG-DSC-FTIR-MS联用技术,通过对分解温度、放热量、分解产物等特征参数进行分析,明确3种推进剂的非等温热分解行为。采用微热量热法,在与甲基紫试验相同温度下对3种推进剂进行等温热分解行为研究。结果 含Al改性双基推进剂在程序升温条件下的热质量损失和热分解行为与普通双基推进剂的基本一致。含RDX改性双基推进剂中的NG较其他2种推进剂更易挥发,相应分解反应初期NG分解释放的NO_(2)较少,且在整个热分解反应历程中分2个阶段,含硝酸酯基团的NC/NG体系先分解,再引起硝铵炸药RDX的热分解。在等温条件下,3种推进剂在40 min对应的反应深度均不超过0.4%,5 h对应的反应深度均不超过3%。但在分解反应初期,含Al改性双基推进剂分解反应的速率更快。结论 对比不同推进剂甲基紫安定性试验结果,并不是甲基紫试纸完全变色时间越长的热安定越好,说明甲基紫安定性试验方法存在一定的局限性。采用分解反应深度作为量气和量热方法转换的纽带,有望采用微热量热作为甲基紫试验的替代技术实现安定性的定量评价。

固体添加物粒径对改性双基推进剂力学性能的影响

为研究某型水下武器发射装置中的改性双基推进剂的力学性能,通过调整固体添加物粒径,对比分析不同粒度Al粉和不同粒度SiC/Al_(2)O_(3)的改性双基推进剂力学性能。结果表明,在Al/SiC推进剂中,推进剂的常温抗拉强度和常温最大伸长率随着Al粉粒径的增大呈现先降低后增大的趋势;在不同Al粉粒径下,推进剂的力学性能随SiC粒度变化趋势不同。Al粉粒径为20μm,SiC粒度为W2.5时,低温和常温抗拉强度最大,分别为37.5 MPa和6.58 MPa;Al粉粒径为140μm,SiC粒度为W1.5时,高温抗拉强度最大,为2.22 MPa;加入Al_(2)O_(3)替代SiC后,低温抗拉强度最大为38.3 MPa,比SiC作为弹道稳定剂的推进剂高2.1%,常温抗拉强度最大值高7.1%,高温抗拉强度最大值高4.3%。可见通过调整固体添加物Al粉和SiC/Al_2O_(3)粒径,可实现对改性双基推进剂的力学性能进行局部调控,为水下发射装置的推进剂配方设计提供有效手段。

涵道螺旋桨多工况设计

单一工况下设计的涵道螺旋桨通常不能满足垂直起降飞机的多工况高效需求。基于叶素动量理论可以开展涵道螺旋桨多工况设计,其关键在于不同工况下螺旋桨拉力占比、修正来流速度的计算。在无螺旋桨几何的情况下,采用动量源方法对涵道拉力进行估算,提出了修正来流速度的计算方法,基于最小能量损失原则建立螺旋桨几何,采用多重参考系方法进行耦合计算流体力学(computational fluid dynamics,CFD)修正,得到单一工况下弦长扭转角关系、螺旋桨拉力占比以及修正来流速度。通过改变设计升力系数及转速,使不同工况下涵道螺旋桨的弦长及扭转角相匹配。分析结果表明,动量源方法计算的涵道拉力占比较大,来流速度修正方法可减少相同工况下耦合CFD求解计算量。多工况设计可有效提高涵道螺旋桨的综合效率。

改性双基推进剂压伸成型工艺安全的数值模拟

为了深入研究压伸工艺参数对改性双基推进剂成型过程安全性能的影响,对压缩熔融段、熔体输送段和口模成型段进行整体建模,对改性双基推进剂物料的密度、流变特性等物料参数进行了测定;基于Polyflow软件,对流体域网格无关性进行了验证,研究了改性双基推进剂物料在非等温条件下压伸过程的安全特性。结果表明,螺杆转速的增加会使物料温度、压力、剪切速率升高,存在燃爆风险,为保证安全性,压伸成型过程中适宜的螺杆转速为10 r/min;螺杆温度增加,剪切速率降低,物料的塑化程度会变差,温度升高易使物料分解,结合改性双基推进剂敏感物料成分特性考虑,螺杆温度为85℃时相对安全;相较于螺杆温度,套筒温度的变化对物料流场的影响较小,结合改性双基推进剂实际生产条件考虑,70℃套筒保温温度适合改性双基推进剂生产。结合模拟结果,得出在推进剂生产过程中需注意压力和温度快速变化带来的影响。

纳米级碳酸铅在NEPE推进剂中的应用

研究了纳米级碳酸铅对NEPE推进剂燃速压力指数的影响。采用DSC分析了纳米级碳酸铅与NEPE推进剂主要组分硝酸酯的相容性以及对推进剂固化反应的催化作用和对高氯酸铵、硝胺常压热分解的催化作用,并利用恒压静态燃速仪测试了推进剂在4MPa～11MPa的燃烧速度和燃速压力指数。发现纳米级碳酸铅表现出与硝酸酯良好的相容性,对推进剂的固化反应和硝胺的热分解均有很强的催化作用,对高氯酸铵的热分解则没有明显的影响。当纳米级碳酸铅应用到NEPE推进剂中时,推进剂的燃速压力指数显著降低。

硼粉改性对推进剂工艺性能的影响

采用HAAKE粘度计测定硼粉/丁羟简单体系和实验推进剂药浆屈服值和表观粘度,研究了硼粉的处理效果和处理硼粉BS对硼含量为35%～40%实验配方药浆工艺性能的影响.结果表明:在研究处理硼粉BD、BW、BT和BS系列中,BS的处理效果最好,处理工艺稳定.用处理硼粉BS制成的实验药浆具有较好的可浇性、流平性和适用期.实验药浆的流体特征,在出料初期2～3 h内呈Casson或Bingham流体,有显著剪切稀化和明显的静止结构恢复特征.

浇铸型高能CMDB推进剂的力学性能

研究了硝化棉种类和含量、高氯酸铵粒径,以及双基球和黑索今含量等对复合改性双基(CMDB)推进剂力学性能的影响。结果表明,随着含氮量12.0%的NC的降低,CMDB推进剂20℃和50℃下的拉伸强度和延伸率均显著降低。在CMDB推进剂中添加适量含氮量13.0%的NC和12.6%的NC均有助于提高推进剂拉伸强度;含氮量13.0%的NC不利于改善推进剂的延伸率;而含氮量12.6%的NC有助于提高推进剂的低温延伸率,但对推进剂高温延伸率影响不显著。在CMDB推进剂中添加适量的双基球对提高推进剂的拉伸强度和延伸率均有利。AP的粒径对CMDB推进剂力学性能影响显著,小粒径的AP有利于提高推进剂的拉伸强度,而大粒径的AP有利于改善推进剂的延伸率。随着RDX取代AP量的逐渐增大,CMDB推进剂在高温和常温下的拉伸强度先增大后减小,而延伸率先增减小后增大。

含能增塑剂PDADN合成及性能研究

介绍了一种新型含能的叠氮类增塑剂ＰＤＡＤＮ 合成、结构及物理化学性质，系列热分析实验表明，它有利于双基组分及黑索今的热分解，指出它在改性双基推进剂中将可改善燃烧性能。

有机铅盐对高能改性双基推进剂燃烧性能和热分解的影响

研究了3种有机铅盐燃烧催化剂NTo铅（NTO-Pb）、水杨酸铅（Sa-Pb）和硬脂酸铅（St-Pb）对高能改性双基推进剂（HEMDB）不同压强下的燃烧性能和热分解的影响。结果表明，有机铅盐燃烧催化剂对HEMDB推进剂的燃烧性能和DSC特征量均有影响；NTO-Pb、Sa-Pb和St-Pb可促进HEMDB推进剂中RDX的热分解；HEMDB推进剂的燃速和DSC特征量均随压强的升高而增大，在1～10MPa压强下该类推进剂的燃速与DSC特征量线性相关。