Computational design of tetrazolone‐based high‐energy density energetic materials: Property prediction and decomposition mechanism

The density functional theory methods are used to design a series of new highly energetic tetrazolone‐based molecules by the combination of the linked tetrazolone framework and versatile substitutes. The molecular and electronic structures, physicochemical, and energetic properties were analyzed and predicted. The decomposition mechanisms were computationally simulated, and 3 potential decomposition channels were proposed. These newly designed tetrazolone‐based compounds show high densities (up to 2.08 g/cm³) and highly positive heats of formation (407.0‐1377.9 kJ/mol) due to all right content of nitrogen and oxygen. Most of them exhibit good detonation velocity (8.31‐9.62 km/s) and detonation pressure (32.40‐43.86 GPa), and some are comparative to excellent explosive CL‐20. Results show that compounds 6 , 10 , 11 , 12 , 15 , 16 , 17 , 22 , 23 , and 24 own superior detonation performance than widely used explosive HMX and may be promising candidates of green high‐performance energetic materials.     

Formation of double front detonations of a condensed-phase explosive with powdered aluminium

The performance characteristics of aluminised high explosive are considered by varying the aluminium (Al) mass fraction in a hybrid non-ideal detonation model. Since the time scales of the characteristic induction and combustion of high explosives and Al particles differ, the process of energy release behind the leading detonation wave front occurs over an extended period of time. Two cardinal observations are reported: a decrease in detonation velocity with an increase in Al mass fraction and a double front detonation (DFD) feature when anaerobic Al reaction occurs behind the front. In order to simulate the performance characteristics due to the varying Al mass fraction, the tetrahexamine tetranitramine (HMX) is considered as a base high explosive when formulating the multiphase conservation laws of mass, momentum, and energy exchanges between particles and HMX product gases. While experimental studies have been reported on the effect of Al mass fraction on both gas-phase and solid-phase detonations, the numerical investigations have been limited to only gas-phase detonation for the varying Al particles in the mixture. In the current study, a two-phase model is utilised for understanding the volumetric effects of Al mass fraction in condensed phase detonations. A series of unconfined and confined rate sticks are considered for characterising the performance of aluminised HMX with a maximum Al mass fraction of 50%. The simulated results are compared with the experimental data for 5–25% mass fractions, and the higher mass fraction behaviours are consistent with the experimental observations.     

Calibration of the Pseudo-Reaction-Zone model for detonation wave propagation

An approach for the calibration of an advanced programmed burn (PB) model for detonation performance calculations in high explosive systems is detailed. Programmed burn methods split the detonation performance calculation into two components: timing and energy release. For the timing, the PB model uses a Detonation Shock Dynamics (DSD) surface propagation model, where the normal surface speed is a function of local surface curvature. For the energy release calculation and subsequent hydrodynamic flow evolution, a Pseudo-Reaction-Zone (PRZ) model is used. The PRZ model is similar to a reactive burn model in that it converts reactants into products at a finite rate, but it has a reaction rate dependent on the normal surface speed derived from the DSD calculation. The PRZ reaction rate parameters must be calibrated in such a way that the rate of energy release due to reaction in multi-dimensional geometries is consistent with the timing calculation provided by the DSD model. Our strategy for achieving this is to run the PRZ model in a detonation shock-attached frame in a compliant 2D planar slab geometry in an equivalent way to a reactive burn model, from which we can generate detonation front shapes and detonation phase speed variations with slab thickness. In this case, the D _n field used by the PRZ model is then simply the normal detonation shock speed rather than the DSD surface normal speed. The PRZ rate parameters are then iterated on to match the equivalent surface front shapes and surface phase speed variations with slab thickness derived from the target DSD model. For the purposes of this paper, the target DSD model is fitted to the performance properties of an idealised condensed-phase reactive burn model, which allows us to compare the detonation structure of the calibrated PRZ model to that of the originating idealised-condensed phase model.     

Generalised expressions for the association and dissociation rate constants of molecules with multiple binding sites

ABSTRACT

Many proteins exhibit multiple binding patches. A patch may harbour a key chemical modification site, but may also simply act as a trap for the binding to another site. Here we consider the scenario in which one molecule (enzyme) binds another molecule (substrate) which contains two sites. We present microscopic expressions for the rate at which the enzyme binds to a particular site on the substrate, both for the scenario in which the enzyme directly binds the site without first visiting the other site, and for the case in which it may visit the other site an arbitrary number of times before binding to the site of interest. We also present the expressions for the corresponding dissociation reactions. These expressions can be used to compute in a single rare-event simulation of the dissociation pathway not only both the intrinsic and effective dissociation rate constants but also both association rate constants.     

诱导空间非相干束匀滑技术的近区特性及改善技术

诱导空间非相干技术是面向激光驱动惯性约束核聚变的一种具有自身独特优势的束匀滑方法.然而直接使用诱导空间非相干方法将引起强烈的近区强度空间调制,这将威胁装置的运行安全,并严重限制装置的最大输出能力.这也是该方法应用于聚变级高功率激光装置的主要技术障碍之一.本文介绍了一种通过双透镜滤波系统对诱导空间非相干束匀滑技术导致的近区空间强度调制进行匀滑的技术.利用该技术可以在保留诱导空间非相干束匀滑方法的先天优势(更好的远区匀滑特性)的前提下,获得均匀、稳定的近区强度分布,从而避免高功率激光系统在使用诱导空间非相干束匀滑技术时,因为近区强度不均匀、不稳定导致的器件损伤及输出能力受限.在理论建模和数值分析的基础上,以近区调制度、软化因子和透过率为主要评价指标,对比分析了方形、圆形、高斯型等3种滤波孔在不同尺寸下的近区输出效果,最终给出了一种典型的优化结果:16×16诱导空间非相干分割数、0.8倍衍射极限宽度、方形小孔.此时近区强度分布均匀,同时保证了较好的远区匀滑效果和高的能量利用率.在此基础上,针对装置的实际应用情况,进一步分析了准直误差对近区强度分布的影响,结果表明准直误差小于0.1倍衍射极限便不会影响输出的近区质量.对诱导空间非相干束匀滑方法所得焦斑的模拟分析表明,滤波系统的加入能进一步改善焦斑的低频不均匀性.     

Numerical simulation of oxide nanoparticle growth characteristics under the gas detonation chemical reaction by space-time conservation element–solution element method

Under harsh conditions (such as high temperature, high pressure, and millisecond lifetime chemical reaction), a long-standing challenge remains to accurately predict the growth characteristics of nanosize spherical particles and to determine the rapid chemical reaction flow field characteristics. The growth characteristics of similar spherical oxide nanoparticles are further studied by successfully introducing the space-time conservation element–solution element (CE/SE) algorithm with the monodisperse Kruis model. This approach overcomes the nanosize particle rapid growth limit set and successfully captures the characteristics of the rapid gaseous chemical reaction process. The results show that this approach quantitatively captures the characteristics of the rapid chemical reaction, nanosize particle growth and size distribution. To reveal the growth mechanism for numerous types of oxide nanoparticles, it is very important to choose a rational numerical method and particle physics model.     

DFT study on the effect of relative positions of methyl-, nitro- and N→oxide groups on the molecular structure,thermal/kinetic stability,crystal density,heat of decomposition and performance characteristics of triazolones

Methyl-, nitro- and N→oxide substituted triazolones are of interest in the contest of high-energy density compounds and have been found to have true local energy minima at the B3LYP/aug-cc-pVDZ level. The optimised structures, harmonic frequencies and thermodynamic values for all the model molecules have been obtained in their ground state. The velocity of detonation (D) and detonation pressure (P) have been evaluated by the Kamlet–Jacob equations using the crystal density and the heat of explosion. The estimated performance properties are higher (D = 9.92–10.27 km/s, P = 48.10–52.52 GPa) compared with 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (D = 9.20 km/s, P = 42.0 Gpa). The higher densities are possibly due to the intramolecular hydrogen bonds and the layered structures in the crystal lattice. We speculate that the calculated heat of explosion and the density are for the gas phase compounds and in the reality they should be for the solid phase which would diminish the magnitude of the calculated values. The –N→O and –NO₂ group leads to the desirable consequences of higher heat of explosion and diminished sensitivities. The substituting of N–H hydrogen atom(s) of triazolones for a –CH₃ group decreases melting point, heat of formation and density; however, the methyl group increases the thermal stability.     

基于磁偶极子构造法几何建模的铁管磁异常正演

地下铁磁性金属管线受地球原磁场磁化产生磁场会改变原地磁场分布,而形成地磁异常;通过管道几何建模和磁偶极子构造法对管道磁异常进行正演分析;首先利用近似的立方体单元对管道进行几何建模并输出相应的立方体单元体积和中心坐标;然后将立方体单元近似为磁偶极子,使用磁偶极子构造法进行管道磁异常正演;最后研究了距径比,磁倾角,磁偏角,地球场强,管道材料磁化率对管道磁异常正演的影响;研究结果表明:在6倍距径比外,同一球面上测点磁异常值接近一致, 且管道磁异常正演结果不受磁倾角,磁偏角和材料磁化率的影响;随着地磁场强度增大,管道磁异常呈线性增大;研究成果将为自主研发高精度磁异常地下管线探测设备奠定理论基础。     

软体微手鲁棒非线性控制设计

软体驱动器是构建智能软体机器人的基石。然而,由于软体驱动器具有非线性、耦合和不确定性等复杂的特性,如何对其进行有效建模与控制是目前极需解决的难题。以一种由三支单腔双向弯曲软驱动器构成的软体微手为研究对象,对其进行了鲁棒非线性控制设计研究。首先,进行了鲁棒非线性控制系统的总体结构设计分析。其次,对如何设计算子控制器、跟踪控制器、算子观测器实现其对软体微手的弯曲角度和力进行控制进行了分析和讨论。接着,分析和研究了鲁棒稳定和跟踪条件。最后,通过基于实验数据的仿真验证了所提方案的可行性和有效性。     

CL-20混合炸药的爆轰波结构

基于爆轰数值模拟计算,分析了CL-20混合炸药爆轰反应的特征,设计了炸药与窗口的界面粒子速度测量实验装置;采用激光干涉法,测量了C-1炸药(CL-20/粘合剂/94/6)与窗口的界面粒子速度; 运用先求导、再分段拟合的方法,对界面粒子速度随时间的变化曲线进行了数据处理,确定了炸药爆轰CJ点对应的时间位置;根据CJ点对应的粒子速度,计算获得了炸药的爆轰反应区宽度和CJ爆轰压力。结果显示:密度为1.943 g/cm3的C-1炸药的爆轰反应时间为38 ns,CJ压力为34.2 GPa。