三维无溶剂含能Ag-MOF的制备、热分解动力学及爆炸性能

Solvent molecules can significantly reduce the heat of detonation and stability of energetic metal-organic framework (EMOF) materials, and the development of solvent-free EMOFs has become an effective strategy to prepare high-energy density materials. In this study, a solvent-free EMOF, [Ag₂(DTPZ)]_n (1) (N% = 32.58%), was synthesized by reacting a high-energy ligand, 2, 3-di(1H-tetrazol-5-yl)pyrazine (H₂DTPZ), with silver ions under hydrothermal conditions, and it was structurally characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, and thermal analysis. In 1, the DTPZ²⁻ ligands that adopted a highly torsional configuration bridged the Ag⁺ ions in an octadentate coordination mode to form a three-dimensional framework (ρ = 2.812 g∙cm⁻³). The large steric effect and strong coordination ability of DTPZ²⁻ effectively prevented the solvent molecules from binding with the metal centers or occupying the voids of 1. Moreover, the strong π-π stacking interactions [centroid-centroid distance = 0.34461(1) nm] between the tetrazole rings in different DTPZ²⁻ ligands provided a high thermal stability to the framework (T_e = 619.1 K, T_p = 658.7 K). Thermal analysis showed that a one-step rapid weight loss with intense heat release primarily occurred during the decomposition of 1, suggesting potential energetic characteristics. Non-isothermal thermokinetic analyses (based on the Kissinger and Ozawa-Doyle methods) were performed using differential scanning calorimetry to obtain the thermoanalysis kinetic parameters of the thermodecomposition of 1 (E_a = 272.1 kJ·mol⁻¹, E_o = 268.9 kJ·mol⁻¹; lgA =19.67 s⁻¹). The related thermodynamic parameters [enthalpy of activation (ΔH^≠ = 266.9 kJ·mol⁻¹), entropy of activation (ΔS^≠ = 125.4 J·mol⁻¹·K⁻¹), free energy of activation (ΔG^≠ = 188.3 kJ·mol⁻¹)], critical temperature of thermal explosion (T_b = 607.1 K), and self-accelerating decomposition temperature (T_SADT = 595.8 K) of the decomposition reaction were also calculated based on the decomposition peak temperature and extrapolated onset temperature when the heating rate approached zero. The results revealed that 1 featured good thermal safety, and its decomposition was a non-spontaneous entropy-driven process. The standard molar enthalpy for the formation of 1 was calculated to be (2165.99 ± 0.81) kJ·mol⁻¹ based on its constant volume combustion energy determined using a precise rotating oxygen bomb calorimeter. Detonation and safety performance tests revealed that 1 was insensitive to impact and friction, and its heat of detonation (10.15 kJ·g⁻¹) was higher than that of common ammonium nitrate explosives, such as octogen (HMX), hexogene (RDX), and 2, 4, 6-trinitrotoluene (TNT), indicating that 1 is a promising high-energy and insensitive material.     

爆炸载荷下脆性颗粒体系破碎特性的数值研究

试验发现,以球形TNT为中心爆源,球形玻璃珠构成的颗粒和球壳中发生破碎的颗粒体积分数随当量比(颗粒球壳的质量与TNT炸药的质量比)的增加呈现指数衰减规律。采用有限元与离散元耦合的连续非连续数值方法,揭示了中心炸药起爆后颗粒环壳内爆炸波的传播衰减和在环壳外界面反射后的稀疏卸载过程。由于爆炸波的短脉冲特性,颗粒内部应力场始终处于应力非均衡状态,采用应力均衡状态下颗粒破碎强度的Weibull分布会得到远高于试验测得的破碎颗粒体积分数。因此采用破坏波传播特征时间内的平均诱导应力而非瞬时诱导应力作为颗粒破碎强度的应力指标,并通过试验结果确定破坏波传播特征时间。考虑了应力传播的非均匀性对于颗粒破碎的影响,得到了平均诱导应力峰值的概率分布随比例距离的变化规律,结合修正后的颗粒破碎强度Weibull分布建立了破碎颗粒体积分数随比例距离的变化模型。     

关于反中心对称矩阵的某些性质探讨

利用反中心对称矩阵的定义以及翻转矩阵等技巧,给出了反中心对称矩阵的伴随矩阵、特征值及特征向量的一些新结论.     

р-Laplace算子基本特征值率的估计

通过改进已有方法,给出了Euclid空间Rν中р-Laplace算子Dirichlet特征值问题中基本特征值率的两个估计,其中一个估计与区域有关,另一个则与区域无关.这里的结论是对已有文献中结果的改进.     

极大加可约矩阵的谱与周期时间向量的关系

提出了极大加代数上可约矩阵特征值的缺失值及冗余值的概念,得到了相应的定理;对特征值与周期时间向量分量之间的关系作了深入的研究.     

解二阶椭圆本征值问题的有限元插值校正方法

§1.引言 本文介绍解二阶椭圆本征值问题的有限元插值校正方法.理论分析和数值实验都表明,此方法具有低代价和高精度的特点.这个方法是超收敛和迭代伽略金法的思想相结合的产物。 考虑二阶椭圆本征值问题:     

Compton散射下强激光等离子体空气冲击波波前的传输特性

 根据球对称激光等离子体空气冲击波在自由空间中传输的约束条件，对多光子非线性Compton散射的强激光等离子体空气冲击波波前的传输特性进行了研究，给出了散射下空气冲击波波前的运动方程，并进行了数值模拟。结果表明：该冲击波的衰减过程不仅与爆炸源和爆炸过程的特性、释放总能量、空气的弹性有关，而且还与散射有关，散射效应使冲击波的初始半径增大，衰减过程加快，能量转移率提高；数值模拟与实验结果符合得很好。     

映照z■e~(az+bz~2)(a,b∈IR)的动力系统 (Ⅰ)爆炸区域

我们拓广了Devaney R.L.关于爆炸线段的定义,定义了系统g(a,b)(z)的爆炸区域,并确定了(a,b)一平面上两个爆炸区域,D_C~o和D_C~∞.文末我们提出了如下猜测D_C=D_C~o∪D_C~∞其中D_C是系统g(a,b)(z)的爆炸点集.     

两级螺旋型爆炸磁通量压缩发生器串联的理论计算

从电路方程出发，对柱形与锥形螺旋型爆炸磁通量压缩发生器(MFCG)的串联进行了计算。通过计算与实验的比较，确定了MFCG内部损耗系数A值；并确定了两级MFCG之间各参数值的关系。     

矩阵乘积的Schur余的奇异值估计

本文得到了矩阵乘积的Ｓｃｈｕｒ余的奇异值的一些不等式，改进了近期的一些结果．