含能材料物理化学性能理论预估研究进展

从含能材料领域的最近发展成果出发,讨论了该领域的主要研究方向,重点论述了当前含能材料物理化学性能理论预估的最新成果,主要包括量子化学、分子动力学或者半经验QSPR建模的方法预估含能材料的感度、燃烧爆轰性能、反应活性、固化机制与力学性能的研究进展。总结了目前存在的主要技术壁垒,包括缺乏完备统一的含能材料性能标准实验数据库,没有自主知识产权的商业化含能材料性能计算软件,且国际上商业软件对含能材料的物理化学性能的可靠预测仅局限于爆轰性能和燃烧性能。文献调研表明,我国需要进一步加强该领域研究,最终建立一个能评价含能材料性能与安全的综合软件平台。     

基于有机阴离子的含能离子盐研究进展

从合成与性能方面概述了包括基于咪唑、吡唑、三唑、四唑、三嗪和四嗪类阴离子、硝基苯类阴离子和非芳香硝基有机阴离子的含能离子盐的研究进展。介绍了含能离子盐在推进剂及熔铸炸药用TNT替代物方面的研究进展。附参考文献101篇。     

氮杂环类含能离子盐和离子液体的研究进展

综述了近年来以唑类、嗪类和呋咱类氮杂环化合物为母体的一些含能离子盐和含能离子液体的合成及其熔点、密度、爆轰等性能.总结了不同取代基对含能离子盐的理化性质的影响,以及如何通过引入不同官能团来设计修饰目标化合物.对一些性能较好的含能离子盐的应用以及含能离子液体的设计进行了展望.     

升华焓的密度泛函理论研究

采用Politzer经验公式,运用密度泛函理论研究了升华焓的预估方法。基于在B3LYP/6–31G**水平上获得56种化合物稳定构型的基础上,运用Multiwfn软件对分子表面进行了定量分析。对比研究了采用Politzer系数和Rice系数对升华焓预估值的影响,结果表明,Politzer系数和Rice系数所造成的最大误差分别为46.1 kJ/mol和38.9 kJ/mol。为了缩小误差,根据34种化合物升华焓的实验值拟合出了一组新的系数(0.000 409(α),2.005 0(β),–2.82(γ)),并用来计算了22种含能化合物的升华焓。计算结果表明,该组新系数使计算值的最大误差为32.6 kJ/mol,标准偏差为13.8 kJ/mol。     

基于二硝酰胺阴离子的非金属含能离子盐研究进展

基于二硝酰胺阴离子的非金属含能离子盐在高能炸药与推进剂方面具有良好的应用前景,其中二硝酰胺铵(ADN)与N-脒基脲二硝酰胺盐(FOX-12)已成为人们最看好的含能材料。介绍了二硝酰胺非金属含能离子盐及其原料的合成方法,总结了二硝酰胺非金属含能离子盐的物化性能,并对一些有潜力的二硝酰胺含能离子盐的爆轰性能参数进行了理论计算。     

钝感高能含能离子盐的研究进展

综述了四唑类、三唑类、咪唑和吡唑类、嗪类和硝基苯类以及非芳香类钝感高能含能离子盐的合成及熔点、热分解温度、密度、生成焓、撞击感度、爆压和爆速等性能。重点讨论了可作为RDX替代物的钝感高能含能离子盐的结构,并展望了其发展前景。附参考文献65篇。     

含能羟基吡啶铅铜盐用作RDX-CMDB推进剂的燃烧催化剂

研究了6种含能羟基吡啶铅、铜盐对RDX-CMDB推进剂燃烧性能的影响。研究发现：含硝基的羟基吡啶铅盐具有较好的催化燃烧作用和降低压强指数的能力,尤其是2-羟基-3,5-二硝基吡啶铅盐,其催化效率最高,含能羟基吡啶铜盐的催化作用不明显。2-羟基-3,5-二硝基吡啶铅盐和4-羟基-3,5-二硝基吡啶铅盐催化效果产生差异的原因是两者热分解历程不同,最后生成的碳量不同。     

用人工神经网络法预估高氮化合物的生成焓

采用误差反向传播学习(BP)人工神经网络算法,以分子结构中不同基团作为描述码,对高氮化合物的标准生成焓进行预估,研究了网络参数及分子结构描述码对标准生成焓的影响,计算结果与文献值符合得较好,其回归方程相关系数为0.99823,相对误差在10%左右.人工神经网络(ANN)法是一种简单有效的预测高氮化合物生成焓的方法.     

［Eu（NTO）_3（H_2O）_5］·5H_2O的热力学性质

通过３硝基１，２，４三唑５酮（ＮＴＯ）铕盐［Ｅｕ（ＮＴＯ）３（Ｈ２Ｏ）５］·５Ｈ２Ｏ在水中溶解焓的测定，算得其标准生成焓、晶格焓、晶格能和标准脱水焓     

低熔点含能化合物研究进展

综述了苯环类、氮杂环类、氮氧杂环类、烷烃类及含能离子盐类低熔点含能化合物的国内外研究现状、合成方法、物理化学性质与爆轰性能,并分析了其性能优劣及实际应用所面临的问题等,对比不同分子主体结构和官能团对化合物性能的影响,探索今后含能材料的重点研究方向以便设计出更好的低熔点化合物,更好地满足熔铸炸药应用要求。指出DFTNAN、DNP、DNBF、BOO、BODN、TNTON等化合物性能优良,可以作为取代TNT作为新型熔铸炸药载体;可以尝试以四唑为基础原料,引入不同性能优良的基团,如：—N₃、—F、—ONO₂、—NHNO₂等,设计新型低熔点含能化合物。附参考文献114篇。     

Influence of laser wavelength on the critical energy density for initiation of energetic materials

Critical densities of the energy of laser initiation of PETN containing nanoscale aluminum inclusions at radiation wavelengths of 1064 and 532 nm were measured experimentally. The critical initiation-energy density that corresponds to a 50%th probability of explosion was 1.15 J/cm² for the first harmonic of a neodymium laser and 0.7 J/cm² for the second. The dependence of the efficiency of radiation absorption by aluminum on the size of metal nanoparticles for the first and second harmonics of a neodymium laser is calculated. It is shown that the particle diameter corresponding to the absorption efficiency maximum and the amplitude of the maximum depend on the radiation wavelength. The absorption efficiency maximum for the first harmonic is observed in an inclusion 204 nm in diameter, and for the second, in an inclusion 96 nm in diameter. The amplitude of the maximum increases from 0.351 at a wavelength of 1064 nm to 0.490 at a wavelength of 532 nm. Dependences of the critical initiation energy density for energetic materials on the radius of metallic nanoparticles are calculated. Qualitative agreement between theoretical and experimental results is shown.     

含能添加剂对含NNHT的CMDB推进剂能量特性影响

利用能量计算程序计算了含高氮化合物2–硝亚胺基–5–硝基–六氢化–1,3,5–三嗪(NNHT)的复合改性双基(CMDB)推进剂(NNHT–CMDB推进剂)的能量特性,并研究了分别用含能添加剂黑索今(RDX)、六硝基六氮杂异伍兹烷(HNIW)和铝粉部分取代NNHT–CMDB推进剂中的NNHT对推进剂能量特性的影响规律。结果表明:无论推进剂中是否含铝粉,NNHT含量增加,将不同程度地降低原CMDB推进剂的各能量特性参量;与RDX相比,HNIW与NNHT搭配使用效果更佳,原NNHT–CMDB推进剂的标准理论比冲提高十分明显;当m(NNHT)∶m(HNIW)=18∶20时,推进剂的标准理论比冲高于含质量分数26%RDX的RDX–CMDB推进剂;当NNHT与HNIW质量比值不变时,含铝推进剂的各能量特性参量明显高于无铝推进剂;添加HNIW后,10 MPa时,NNHT–CMDB推进剂的标准理论比冲分别可达到253.4 s(无铝)和261.9 s(含铝质量分数5%)。     

合理利用自用碱大力节约能源

综合分析了我国氯碱工业自用碱的现状与差距，重点阐述了合理利用自用碱的对策与建议，从而大力节约能源，降低生产成本，提高企业的经济效益。     

含能交联剂对PBT高能推进剂力学性能的影响

以小分子交联剂作对比,重点研究了含能大分子多元醇交联剂PBT(3,3–双(叠氮甲基)氧杂环丁烷与四氢呋喃(BAMO–THF)共聚醚)三元醇(TBT)对PBT高能固体推进剂力学性能的影响。结果表明:1采用小分子交联剂,PBT推进剂具有较高的拉伸强度与模量;同时,小分子交联剂是一种键合剂,可有效阻止推进剂在断裂拉伸时基体与填料之间的"脱湿"。2采用含能大分子交联剂,PBT推进剂具有良好的最大伸长率,但断裂拉伸时推进剂的"脱湿"现象十分严重;随含能交联剂含量的变化,PBT推进剂热稳定性基本不变。     

Cohesive energy density of polytetrahydrofuran

Measurements have been conducted on radiation-crosslinked polytetrahydrofuran (PTHF) of stress-strain and of swelling coefficients in simple esters. For the linear polymer, measurements have been made of density and intrinsic viscosities in the esters. [η] was also determined under the θ conditions of 33.5°C. in diethyl malonate. The results have been incorporated into several (sometimes interdependent) approaches towards the evaluation of the solubility parameter δ_p of PTHF. The mean of the nine values obtained is 8.55 (cal./cc.)^1/2, whence the cohesive energy density is 5.17 kcal./mole. Seventeen experimental values of the Flory interaction parameter χ are also reported.     

The role of energy density

Dietary energy density (ED) appears to have a major influence on the regulation of food intake and body weight. If people consume a fixed weight of food each day, then high-ED diets should be associated with high energy intakes and with overweight. In contrast, low-ED diets should result in lower daily energy intakes and therefore weight loss. For this approach to work, low-ED foods must be as palatable as high-ED foods and, calorie for calorie, have a greater satiating power. Each of those assumptions is debatable. Dietary ED depends chiefly on the water content of foods. As a rule, high-ED foods are more palatable but less satiating, whereas low-ED foods are more satiating but less palatable. Consumer preferences for high-ED foods can be explained in terms of good taste, low cost, and convenience. Low-ED foods, such as fresh produce, provide less energy per unit cost than do high-ED foods, which often contain added sugars and fats. Poverty and obesity may well be linked through the habitual consumption of a low-cost, high-ED diet.     

Prediction of nonrandom mixing in lattice model with multi-references

A new lattice theory is proposed to describe nonrandom mixing behavior based on recently developed lattice model theory by Aranovich and Donohue. The present theory assumes multi-references in order to take into account interference effects on non-random mixing among pairs. The number of references was obtained from Monte Carlo simulations for monomer+hole mixtures. Monte Carlo simulation for hole [0]+monomer [1]+monomer [2] mixture shows that this theory is more accurate than Guggenheim’s quasi-chemical theory or the Aranovich-Donohue model in a wide range of temperatures and densities. Especially, even under the stringent condition of zero interaction energy parameter ε₁₂=0, the present theory predicts well the extent of nonrandom mixing. For dimer fluid the non-randomness is calculated using the surface fraction. Here three references was used as in the case of monomer fluid with chain connectivity constraints. Comparison of the theory with Monte Carlo simulation results for dimer+hole system shows a good agreement.     

超声能量密度对污泥脱水性能的影响

<正>引言近年来,生物法在城市污水处理中得到广泛的应用,然而在处理过程中产生了大量的污泥,污泥中含有50%～70%的有机物和较多的氮、磷等营养成分以及致病菌、寄生虫卵等有害物质。其化学     

环氧树脂密度与二面角扭转能的仿真计算

基于COMPASS分子力场,利用分子动力学模拟方法和Materials Studio软件建立了低固化度交联耦合的双酚A型环氧树脂交联结构模型,并利用环氧树脂交联体系模型模拟计算了不同温度下交联环氧树脂的密度和二面角扭转能,以此预测了环氧树脂的玻璃化转变温度(Tg)。结果表明,计算得到的Tg与实验值具有良好的一致性,分子动力学模拟方法可以应用于复杂聚合物体系结构与性质的研究中。     

Improved energy storage density and energy efficiency of Samarium modified PMNT electroceramic

We report the improved energy storage density and efficiency after 2.5% of Samarium substitution in ferroelectric Pb[(Mg_1/3Nb_2/3)_0.80Ti_0.20]O₃ (PMNT) electroceramic. The microstructure and surface morphology were analyzed and correlated with various functional properties. The energy storage density, leakage current density, ferroelectric and dielectric properties were investigated thoroughly, indicating that Samarium's substitution significantly modified the microstructure, the dielectric strength, breakdown electric field, and turned ferroelectric PMNT to relaxor ferroelectrics. Due to the relaxor nature, the gap between remanent polarization and maximum polarization increases with the substitution of Samarium in PMNT matrix, which further increases the recoverable energy storage density and energy efficiency. A nearly 100% increase in recoverable energy density and efficiency was obtained at an electric field strength of 35 kV/cm at room temperature (～296 K). The electroceramic shows maximum energy density near the ferroelectric phase transition temperature (325 K–345 K) region and provides a moderate energy storage density for possible applications in power microelectronics.