A fused heterocyclic high-temperature heat-resistant compound bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine(DATC)was synthesized from 3,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine by substitu-tion,thermolysis and cyclization,and its molecule structure was characterized by elemental analysis,IR,NMR and HRMS anal-ysis.The mechanism of 3,6-bis(1 H-1,2,3,4-tetrazd-5-ylamino)-1,2,4,5-tetrazine(BTATz)thermolysis and cyclization re-action was discussed,and the optimization of reaction conditions was carried out.The morphology of DATC was characterized by SEM.The thermal performance of DATC was characterized by DSC and TGA and the physicochemical and detonation prop-erties of DATC were estimated based on density functional theory.The impact sensitivity and friction sensitivity of DATC were tested using a drop hammer and BAM friction tester.The results showed that DATC had a theorectical density of 1.827 g/cm3,heat of formation of+666.37 kJ/mol,thermal decomposition peak temperature of 477.9℃(DSC,10 ℃/min),theorectical detonation velocity of 7.80 km/s,and theorectical detonation pressure of 27.3 GPa.Its impact sensitivity was higher than 100J,and its friction sensitivity was higher than 360 N.It was well compatible with RDX,HMX,CL-20,4,8-di(2,4,6-trini-trophenyl)difuzan pyrazine(TNBP)and PYX.
The application of 3D printing technology in the performance regulation and control of aluminum-based energetic materials were exposited.The effects of 3D printing ink optimization and microstructure optimization on the burning rate and mechanical properties of molding materials were discussed.It is found that the addition of fluoropolymer or detachable polymer in the ink can significantly affect the initial reaction path of aluminum powder and adjust its ignition and combustion characteris-tics.As a binder in the application of energetic materials,it can rapidly release a large amount of gas products and inhibit the agglomeration of aluminum powder,which is a new path for future binder selection.The microstructure optimization of 3D printing energetic materials mainly utilizes methods such as changing the spatial structure,distribution gradient,and specific structure of components to improve the combustion efficiency of energetic materials.According to the current achievements and development trends,the combination of ink and microstructure optimization will be a potential direction for the manufac-ture process of energetic materials in the future.With 94 references.
To investigate the effect of damage on the reaction growth of 2,4-dinitroanisole(DNAN)based melt-cast explosive after ignition and to obtain the characteristic parameters of reaction growth,five groups of samples with different presets of damage were tested for reaction growth after ignition.In the reaction growth test after ignition,monochromatic light shielding technology was used to shield the strong light interference generated during the explosive reaction process;Using a high-speed camera equipped with a monochromatic light lens to observe and record the entire reaction growth process,and the image e-volution of the explosive reaction growth process was obtained.A pressure testing system was used to test the pressure change process inside the reaction vessel and to obtain the pressure change during the reaction growth process.The results show that the reaction growth process of DNAN-based melt cast explosive after ignition mainly includes ignition,slow reaction and fast reaction.In the test,the ignition delay time of the samples decreases with the increase of damage,except for the samples with 1.26％damage caused by extrusion.The average ignition delay time of the five groups of samples is 1.140ms.The duration of slow reaction decreases to 0 with the increase of damage degree,and the occurrence of damage accelerates the process of reaction growth.In the rapid reaction stage,the reaction duration and maximum pressure in the vessel decrease with the in-crease of damage degree.With the increase of damage degree,the maximum pressure change rate first increases and then de-creases,but it is greater than that of the samples without damage.In the samples with 0.44％damage degree stimulated by high temperature,the maximum pressure change rate is 13.67 MPa/ms.
In order to solve the problem for treating small quantities of waste gun propellants generated during production and use,in the independently established mobile small incinerator of energetic materials,three representative waste gun propellants of single-base,double-base and mixed nitric ester were selected to study the changes of pressure and temperature in the incin-erator and the effect of different flue gas treatment processes on the pollutants generated during incineration,especially NOx(NO and NO2).The results showed that the incinerator burning process was stable,the temperature and pressure in the incin-erator did not appear abnormal,and the incineration process was safe and reliable.The main pollutants of waste gun propel-lants incineration were NOx and CO.The secondary combustion technology was able to basically eliminate CO.The selective non-catalytic reduction(SNCR)technology reduced NOx by 68.56％,achieving ultra-low emission of pollutants.This study provides effective technical ways and means for the safe and clean treatment of small quantities of waste gun propellants.
To investigate the accuracy of the currently used three auxiliary methods(atomization energy,equivalent bonding and isodesmic reaction methods)for calculating the heat of formation(HOF)values,the structure optimization and frequency calculations were performed for 160 kinds of novel energetic molecules at the B3LYP/6-311G(d,p)theoretical level.The molecules were subject to single-point energy calculations at the MP2/6-311++G(d,p)theoretical level.The HOF values were calculated using the three commonly used auxiliary reactions(atomization energy method,equivalent bonding method,and atom equivalent method)by extracting thermodynamic values and electronic energies,where the results were compared with the HOF values directly output by the G4(MP2)-6X method,and the regression coefficients were fitted for each method.The linear regression equation was established,which can be used in combination with B3LYP/6-311G(d,p)//MP2/6-311++G(d,p)theoretical level to obtain the calculation accuracy of G4(MP2)-6X method.The enthalpies of formation of 160 kinds of substances at different theoretical levels and enthalpies of formation calculation methods were calculated.The correla-tion of the three methods was found to be:atomization energy method＞equivalent bonding method＞atom equivalent method.
In order to solve the problems of low charging efficiency and easy crystal transition of polycrystalline main explosives in inkjet printing process,sodium alginate(SA)and water-soluble acrylic ester(AE)were used as a two-component bonding system,and submicron e-CL-20 was used as the main explosive,a CL-20-based micro-nano particle suspension energetic com-posite ink with 40％(mass fraction)explosive particle was designed and prepared,which was molded by inkjet printing process.The surface morphology,main explosive crystal form,thermal stability and mechanical sensitivity were tested by scan-ning electron microscope(SEM),X-ray diffractometer(XRD),differential scanning calorimeter(DSC),BAM friction sensitiv-ity meter and BAM drop weight meter.The micro-detonation performance of the printed samples was tested and analyzed.The results show that the designed energetic ink has good printability.The surface of the molded sample is smooth and the internal structure is uniformly distributed in the shape of multi-microporous honeycomb.The microscopic particle size is about 200-400 nm.The CL-20 explosive has no crystal transition in inkjet printing process,and the crystal form is still ε-type.Compared with the submicron CL-20,the critical impact energy and critical friction force of the printed sample are increased by 0.5 J and 48 N respectively.The thermal decomposition peak temperature increase slightly,exhibiting excellent thermal and mechanical safety.The detonation critical size and detonation velocity of the printed sample are 1 mm X 0.033 mm and 7 348.3 m/s respec-tively,which shows a good detonation ability in micro-scale.
In order to improve the performance of the on-site mixed emulsion explosive,six groups of explosive samples were prepared by adding 0％,3％,6％,9％,12％and 15％in mass fraction of porous granular ammonium nitrate.The micro morphology and structure of porous granular ammonium nitrate were analyzed by scanning electron microscopy.The detonation heat and detonation velocity of the explosives were calculated by B-W method,and the viscosity,density and detonation ve-locity of the explosive samples were tested.The results show that the viscosity of the explosive increases with an increase in the mass fraction of porous granular ammonium nitrate.When the mass fraction is 0％to 12％,the viscosity ranges from 1.75 × 105 mPa·s to 2.97 × 105 mPa·s.The theoretical heat of explosion increases from 2 382.95 kJ/kg to 2 790.89 kJ/kg,and the theoretical detonation velocity increases from 4 229 m/s to 4 683 m/s.The actual detonation velocity first increases from 4 198 m/s to 5 294 m/s and then decreases to 4578 m/s under the influence of charge density.When the mass fraction of por-ous granular ammonium nitrate is 9％,the actual detonation velocity of explosive reaches the highest.When the explosive is applied in the mine blasting,the rock fragmentation decreases after blasting and the ore fines rate increases from 30％to 45％.
The viscosity,yield stress and thixotropy of two typical hydroxyl terminated polybutadiene(HTPB)propellants(low burning rate and medium burning rate)slurries were analyzed by the rotational rheometer.The combined rheometer-infrared spectrometer was adopted to characterize the histories of rheological properties with time of the two slurries and the infrared spectra of the slurries at different curing time.The dynamic thermomechanical analyzer and electronic material testing machine were used to test the dynamic and static mechanical properties of the cured grain column.The results show that viscosity of low burning rate propellant and medium burning rate propellant at the shear rate of 1 s-1 were 621.6 Pa·s and 1 061 Pa·s respec-tively,and the thixotropy values were 124.4 Pa/s and 139.2 Pa/s respectively,indicating that the viscosity and the thixotropy at low burning rate is small.The gel times of low burning rate and medium burning rate propellants are 13 h and 19 h respec-tively,indicating that the curing reaction speed of low burning rate propellant is faster;the a transition peak temperatures of low burning rate and medium burning rate propellants are 26.2 ℃ and-1.3 ℃,p transition peak temperatures(glass transi-tion temperatures)are-60.9 ℃ and-57.7 ℃ respectively.The maximum tensile strength(σm)are 1.01 MPa at 20 ℃,the maximum elongation at break(εm)are 58.4％and 43.8％respectively;σm are 2.58 MPa and 2.63 MPa at-40 ℃,and em are 69.7％and 48.3％respectively,showing that the mechanical properties of low burning rate propellant is better than those of medium burning rate propellant.
1 温压炸药的内涵与特点 温压炸药是一种富燃料炸药,在其爆炸过程中,大量未完全反应的中间产物及金属燃料可以利用空气中的氧发生后燃反应,加强冲击波能的同时以长时间爆炸火球的形式提高整体爆炸能量,形成独特的温压效应.
In order to solve the problems of long rearrangement time,high toxicity of rearrangement reagents and easy subli-mation of N-nitropyrazole(N-NP)in the synthesis of 3-nitropyrazole(3-NP),N-nitropyrazole was used as raw material to pre-pare 3-NP by the hydrothermal method using xylene as the rearrangement solvent,and the structures were characterized by mi-croscope and IR spectrum.The reaction temperature,reaction time,filling degree and other factors were optimized.The re-sults show that the optimal reaction conditions are as follows:reaction temperature of 180℃,holding time of 3 h,filling de-gree of 15％,and the yield of 3-NP at corresponding theoretical pressure of 6.130 MPa is 100％.The product purity is stabi-lized above 99％,showing that the product obtained by this process can be directly used without post-treatment.The product yield is high when the solid-to-liquid ratio(N-NP∶xylene)is 1∶3 in the hydrothermal method.Due to the low consumption,low cost,and low toxicity of rearrangement solvent,the hydrothermal method is expected to replace the traditional synthetic process of 3-NP.
The structural characteristics,synthesis method,crystal characteristics and thermal decomposition performance of perchlorate based molecular perovskite energetic compounds(DAPs)were described.The research status in material modifica-tion and detonation performance were also summarized.The results show that DAPs are mainly synthesized based on the mo-lecular assembly method,through a one-pot reaction from high performance oxidizer and low cost fuel.The perovskite ener-getic compounds(H2dabco)[M(ClO4)3](M=Na+,K+,Rb+,NH4+)correspond to DAP-1,DAP-2,DAP-3,DAP-4,respec-tively,and their crystal morphologies exhibit cube shape.The thermal decomposition peak temperature of DAPs are higher than 350℃,and the excellent thermal stability makes DAPs belonging to heat-resistant energetic materials.The addition of catalyst components can significantly change the thermal decomposition performance of DAP-4((H2 dabco)[NH4(ClO4)3]).In terms of energy performance,the DAPs have comparable detonation performance with RDX.Finally,some proposal about the future direction of the research and development are put forward.It is pointed out that further studies about the DAPs represented by DAP-4 should be performed to understand the unique structure and properties of this material,and expand its application in the field of explosive.With 44 references.
为研究低铝含量推进剂的燃烧特性,以铝粉质量分数5％的低铝含量HTPB推进剂为对象,以铝粉质量分数12％～18％的HTPB推进剂为参比,通过水下声发射、BSFΦ75及BSFΦ165标准试验发动机等测试方法研究了低铝含量推进剂的燃烧性能和能量性能.结果表明,同一固含量条件下,低铝含量推进剂燃速较高,压强指数没有明显变化;铝粉粒度越细,低铝含量推进剂燃速和燃速压强指数越大;经BSFΦ75发动机内弹道p(压力)一t(时间)曲线验证,8～10 MPa内低铝含量推进剂燃烧稳定;经BSFΦ165发动机试车验证,7MPa下,低燃速低铝含量推进剂实际比冲2 387 N·s/kg,比冲效率达到97.3％,高燃速低铝含量推进剂实际比冲2465 N·s/kg,比冲效率达到98.6％.低铝含量推进剂燃烧效率高,相近燃速下低铝含量推进剂与常规铝含量推进剂能量在同一水平.
为了探索聚四氟乙烯(PTFE)对镁和Al12 Mg17反应特性的影响,采用TG-DSC对样品的高温氧化行为进行测试分析;利用自搭建的高速显微观测系统对其燃烧行为进行了精细地观测;使用XRD和SEM等对反应前后样品的结构和组成等进行了分析;使用光谱仪对样品燃烧过程中的光谱辐射特性进行记录.结果表明,当PTFE在空气中加热时,PTFE分别将Mg和Al12 Mg17的起始反应温度提高了283.3℃和368.3℃;Mg与PTFE/Mg样品燃烧过程中,均在490～505 nm间观察到了MgO的辐射峰,在517和518 nm处观察到了镁的辐射峰;与镁原料相比,PTFE/Mg中观察到了更加明显的微爆燃烧.对于Al12 Mg1,PTFE的加入有助于其微爆燃烧的发生,样品燃烧过程中在417.486和512 nm处观察到的AlO辐射峰说明PTFE的加入可以促进Al12Mg17中铝的燃烧.
总结归纳了化学能引燃、光能激发、电磁波、高压冲击波、电能激发以及气固流动换热等6种不同能量激励方式下固体含能材料的点火引燃方法,重点综述了点火引燃技术的性能特点以及其在固体含能材料基础研究方面的研究进展.固体含能材料与点火引燃技术之间具有匹配性,点火引燃技术的选择需综合考虑复杂度、稳定性与集成难度等系统特点,以及点火机理、升温速率、堆积形态等固体含能材料特性.基于固体含能材料在点火燃烧本征机理与点火燃烧控制规律两方面的基础研究需求,指出固体含能材料的点火引燃技术将向更安全可靠高效、可精确控制能量输出与可实现测量装置高度集成等方向发展.未来工作中建议进一步加强含能材料领域的单颗粒点火燃烧本征机理阐明、多种颗粒堆积形态点火燃烧研究体系完善与点火燃烧特性控制策略构建等方面的研究内容.附参考文献112篇.
To prepare porous carbon nanomaterials with high specific surface area and alter the thermal decomposition catalytic performance of HMX and RDX,by using two different dispersing effects of asphaltene oxide as carbon source,two types of porous carbon nanosheets with different pore sizes were obtained by structural guides formed by urea at high temperature.The morphology and structure of the samples were characterized by scanning electron microscopy(SEM),fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS)and specific surface area and pore size analyzer tests.The re-sults show that the carbon nanosheets(ASPCNs 2)prepared from the asphaltene oxide with strong hydrophilic have higher spe-cific surface area(2470.47、1 742.83 m2/g)and larger pore volume(1.38、1.40 cm3/g)than those prepared from the as-phaltene oxide with weak hydrophilicity(ASPCNs 1).ASPCNs 1 and ASPCNs 2 present honeycomb-like structure,and the pore structure is mainly composed of micropores.Besides,the catalytic effects of ASPCNs 2 on the thermal decomposition of RDX and HMX are better than ASPCNs 1.The thermal decomposition peak temperatures of RDX and HMX in the presence of ASPC-Ns 2 are decreased by 26.23℃ and 34.15℃,respectively,and the apparent activation energies are decreased by 37.45 kJ/mol and 48.22 kJ/mol,respectively.
为实现纳米铝热剂复合物反应活性的调节,采用静电喷雾技术制备了一系列不同Al/B 摩尔比的Al/B/CuFe2O4@NC 复合物,并通过XRD、FT-IR、SEM、DSC、激光点火和燃烧实验对复合物的相组成、结构和铝热反应特性进行系统表征分析.DSC 结果表明,纳米B 有益于增加复合物的热释放能和提高其热稳定性,Al/B 摩尔比为5/5 工况下的热释放能由1138.5 增至1426.9J/g,铝热反应温度随B 含量的增加而提高.点火和燃烧实验发现,静电喷雾能显著增强复合物的反应活性,使其点火延迟由16 ms 降至10 ms,燃速由3.34 增至6.01 cm/s;通过改变Al/B 摩尔比,复合物的燃速、燃烧室压力增速和静电火花感度分别在6.01～36.36 cm/s、0.05～0.17 MPa/ms 和61.25～11.25mJ之间可调,而当Al/B 摩尔比小于5/5 时,其点火和燃烧困难,表明B 粉是调节复合物活性的有效添加剂.
为了改善二茂铁基衍生物的燃烧催化性能,向其引入富氮的高能基团,以构建具有良好热稳定性、燃烧催化活性的新型二茂铁基三氮唑化合物.用含三氮唑基团的化合物为原料与二茂铁甲酰氯、二茂铁甲醛反应,分别合成单、双二茂铁基三氮唑化合物,通过1H NMR、13C NMR、X-射线单晶衍射、IR 和UV-Vis对化合物的结构进行表征,并测定其抗氧化性、热稳定性及对AP 的催化性能.结果表明,合成的化合物的电位差值均大于80mV,具有一定的抗氧化性;单二茂铁基三氮唑化合物A1～A4 的热分解温度在200℃左右,双二茂铁基三氮唑化合物A5～A7 的热分解温度在240～380℃,因此后者的热稳定性相对前者更高;化合物对AP 有一定的催化性能,均能引起AP 的两个放热峰不同程度地提前,其中单、双核二茂铁基三氮唑化合物对AP 的低温放热峰分别提前了69～84℃、56～62℃,高温放热峰分别提前了144～165℃、153～184℃.由此得知双核二茂铁基三氮唑化合物对AP 的催化性能优于单核二茂铁基三氮唑化合物.
为了进一步研究高能稠环四嗪的应用性能,采用差示扫描量热(DSC)法和真空安定性实验(VST)对3-硝铵基-6-(1 H-四唑-5-基)-[1,2,4]三唑[4,3-b][1,2,4,5]四嗪(TATTN)及肼盐(TATTN·N2H4)、铵盐(TATTN·NH4)和羟胺盐(TATTN·NH3 OH)与硝酸酯类含能黏结剂的相容性进行初步研究;采用DSC 法对上述相容性好的混合体系的热分解动力学进行研究.DSC 研究结果表明,TATTN 及其铵盐与硝化棉(NC)均相容;TATTN 及其铵盐与吸收药(硝化棉和硝化甘油混合物,NC/NG)均相容;TATTN及其盐与N-硝基二乙醇胺二硝酸酯(DINA)的相容性较差,敏感,不适合使用.VST 实验结果表明,TATTN及其铵盐与NC、吸收药相容.由此可见,TATTN 及其铵盐能与NC 和NC+NG 体系相容.利用氧弹量热法测量获得TATTN、TATTN·N2H4、TATTN·NH4和TATTN·NH3 OH 的燃烧能,进而计算获得生成焓,分别为903.08、1175.76、902.16 和1 020.6 kJ/mol,表明TATTN、TATTN·N2H4、TATTN NH4和TATTN· NH3OH 是具有高的正生成焓的化合物.
为了探讨Al/Cr2O3 纳米铝热剂对硝化棉(NC)热分解过程的影响,采用差示扫描量热法(DSC)及热重/红外联用技术(TG/DTG-FTIR)研究了单组分NC 和Al/Cr2O3/NC复合物的热分解反应过程.运用Kissinger法、Starink法、Kissinger-迭代法和Ozawa-迭代法计算得到NC及Al/Cr2O3/NC 的表观活化能.通过FWO 法、KAS 法和Friedman法得到NC 和Al/Cr2O3/NC热分解过程的动力学参数,并引入修正后的Šesták-Berggren经验方程对相应热分解反应动力学模型进行重建.结果表明,Al/Cr2O3 纳米铝热剂可使NC热分解反应的表观活化能降低33.7 kJ/mol,热点火温度降低3.5℃,热爆炸临界温度降低3.0℃.Al/Cr2 O3/NC 的热分解反应过程遵循n级动力学方程f(a)=7.25α0.73(1-α)2,12.在Al/Cr2O3 催化作用下,NC 首先断裂O—NO2 键,最终释放H2O、CO2、CO、NO2、NO、N2O、HCHO 和HCOOH气体产物.
为了解决延期药在导弹武器系统以及空间飞行器作用过程中暴露出的延期时间不稳定、延期时间漂移过大等问题,提高武器装备系统的使用可靠性和安全性,开展了铜氧化物对钨系延期药燃烧性能催化行为研究.通过扫描电子显微镜(SEM)、差示扫描量热技术(DSC)系统分析了Cu2O以及CuO分别与高氯酸钾混合物的微观形貌与热分解性能,通过延期药发火性能试验验证了新型钨系延期药体系的燃烧性能.结果表明,CuO与Cu2O的加入分别使高氯酸钾(KClO4)热分解峰值温度下降了109.1与103.5℃,对KClO4热分解过程促进作用CuO优于Cu2O;添加有金属氧化物的配方Y-1与Y-2的燃烧速率相比于原始配方(Y-0)均有提高,与混合物热分解过程表现出一致的催化作用规律,CuO的燃烧催化效果与燃烧稳定性均优于Cu2 O.
