Theoretical Insight into the Influence of Molecular Ratio on the Stability, Mechanical Property, Solvent Effect and Cooperativity Effect of HMX/DMI Cocrystal Explosive

Molecular dynamics method was employed to study the binding energies of the selected crystal planes of the 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane（HMX）/1,3-dimethyl-2-imidazolidinone（DMI） cocrystal in different molecular molar ratios. The mechanical properties were estimated in different molar ratios. Solvent effects were evaluated and the cooperativity effects were discussed in the HMX···HF···DMI ternary by using the M06-2x/6-311＋G（2df,2p） and MP2（full）/6-311＋G（2df,2p） methods. The results indicate that the substituted patterns（020） and（100） own the highest binding energies. The stabilities of cocrystals in the 1：1 and 2：1 ratios are the greatest, and thus the HMX/DMI cocrystals prefer cocrystallizing in the 1：1 and 2：1 molar ratios, which have good mechanical properties. The sensitivity change of cocrystal originates from not only the formation of intermolecular interaction but also the increment of bond dissociation energy of the N–NO2 bond. The cooperativity effect appears in the linear complex while the anti-cooperativity effect is found in the cyclic system. DMI binding to HMX is not energetically and structurally favored in the presence of HF. This is perhaps the reason that the solvent with large dielectric constant weakens the stability of the HMX/DMI cocrystals. Therefore, the solvents with low dielectric constants should be chosen in the preparation of HMX/DMI cocrystals.

Evaluation of gases'molecular abundance ratio by fiber-optic laser-induced breakdown spectroscopy with a metal-assisted method

A metal-assisted method is proposed for the evaluation of gases’molecular abundance ratio in fiber-optic laser-induced breakdown spectroscopy(FO-LIBS).This method can reduce the laser ablation energy and make gas composition identification possible.The principle comes from the collision between the detected gases and the plasma produced by the laser ablation of the metal substrate.The interparticle collision in the plasma plume leads to gas molecules dissociating and sparking,which can be used to determine the gas composition.The quantitative relationship between spectral line intensity and molecular abundance ratio was developed over a large molecular abundance ratio range.The influence of laser ablation energy and substrate material on gas quantitative calibration measurement is also analyzed.The proposed metal-assisted method makes the measurement of gases’molecular abundance ratios possible with an FO-LIBS system.

A modeling analysis of molecular orientation at interfaces by polarization-dependent sum frequency generation vibrational spectroscopy

Sum frequency generation(SFG) vibrational spectroscopy has been proven an excellent tool to measure the molecular structures, symmetries and orientations at surfaces/interfaces because of its strong polarization dependence. However, a precise quantitative analysis of SFG spectral intensity and molecular orientation at interfaces must be carefully performed. In this work, we summarized the parameters and factors that are often ignored and illustrated them by evaluating studies of CO adsorption on the(111) facet of platinum(Pt) and palladium(Pd) single crystals at the gas(ultra-high vacuum, UHV)/solid interfaces and methanol(water) adsorption at the air/liquid(solid/liquid) interfaces in the presence of sodium iodide(chloride) salts. To intuitively estimate the influence of incidence angles and refractive indices on the SFG intensity, solely a defined factor of|Fyyz| was discussed, which can be individually separated from the macroscopic second-order non-linear susceptibility χ yyz^(2) term and represents the SSP intensity. Moreover, effects of refractive indices and the molecular hyperpolarizability ratio(R) were discussed in the orientational analysis of interfacial CO and methanol molecules. When IPPP/ISSP was identical, molecules with a larger R had smaller tilting angles(q) on Pt(assuming q < 51°), and CO molecules on Pd would tilt much closer to the surface than they did on Pt. A total internal reflection(TIR) geometry enhanced the SFG intensity, but it also amplified the influence of refractive index on SFG intensity at the solid(silica)/liquid interface. The refractive index and R-value had similar influence on the methanol orientation in the presence of sodium iodide salts at air/liquid and solid/liquid interfaces. This work should provide a guideline for analyzing the orientation of molecules with different R, which are adsorbed on catalysts or located at liquid interfaces involving changes of refractive indices.

Molecular Simulation of Adsorption of Quinoline Homologues on FAU Zeolite

The Grand Canonical Monte Carlo(GCMC) simulation method was used to investigate the adsorption properties of quinoline homologues(quinoline, 2-methyl quinoline, and 2,4-dimethyl quinoline) on the FAU zeolite. The adsorption heat, adsorption isotherms, and adsorption sites of them were obtained. At the temperature ranging from 673.15 to 873.15 K, the Henry constant of quinoline homologues calculated on the FAU zeolite was applied to simulate their adsorption heat. And its value was more in accordance with the related data reported in the literature. The results showed that their isosteric heat decreased in the following order: 2,4-dimethyl quinoline(118.63 kJ/mol) > 2-methyl quinoline(110.45 kJ/mol) > quinoline(98 kJ/mol), and complied with the order of their adsorbate basicity. The competitive adsorption of three components of quinoline homologues on the FAU zeolite was calculated numerically at a temperature of 773.15 K and a pressure range of 0.1—100 MPa under the Universal force field. Their adsorption capacity decreased in the following order: quinoline > 2-methyl quinoline > 2,4-dimethyl quinoline. The smaller the molecule size of the adsorbate, the greater the saturated adsorption capacity would be. It was found that the quinoline homologues could be adsorbed in the main channels of 12- membered-ring framework of the zeolite. Simultaneously, the influence of silica/alumina ratio on the adsorption property of quinoline homologues in FAU zeolite was studied. The smaller the silica/alumina ratio, the greater the isosteric heat and adsorption capacity would be.

Size dependency and potential field influence on deriving mechanical properties of carbon nanotubes using molecular dynamics

A thorough understanding on the mechanical properties of carbon nanotube （CNT） is essential in extending the advanced applications of CNT based systems. However, conducting experiments to estimate mechanical properties at this scale is extremely challenging. Therefore, development of mechanistic models to estimate the mechanical properties of CNTs along with the integration of existing continuum mechanics concepts is critically important. This paper presents a comprehensive molecular dynamics simulation study on the size dependency and potential function influence of mechanical properties of CNT. Commonly used reactive bond order （REBO） and adaptive intermolecular reactive bond order （A1REBO） potential functions were considered in this regard. Young＇s modulus and shear modulus of CNTs are derived by integrating classical continuum mechanics concepts with molecular dynamics simulations. The results indicate that the potential function has a significant influence on the estimated mechanical properties of CNTs, and the influence of potential field is much higher when studying the torsional behaviour of CNTs than the tensile behaviour.

Impact parameter dependence of the yield ratios of light particles as a probe of neutron skin

The yield ratios of neutron/proton(R(n/p)) and ~3H=~3He(R(t/~3He)) with reduced rapidity from 0 to 0.5 are investigated for 50 MeV/u ^(42;44;46;48;50;52;54;56)Ca+^(40)Ca.This was conducted at whole reduced impact parameters using the isospin-dependent quantum-molecular-dynamics model in which the initial neutron and proton densities are sampled within the Skyrme–Hartree–Fock model, using which the neutron skin thickness(△R_(np)) is determined for different neutron-rich Ca isotopes. The results show that both R(n/p) and R(t/~3He) have strong linear correlations with △R_(np) of different Ca isotopic projectiles from five different centralities. It is suggested that R(n/p) and R(t/~3He), from the same centrality, could be treated as possible experimental observables to extract the neutron skin or halo thickness for neutron-rich isotopic nuclei,including the nuclei near the neutron drip line.

Synthesis and Characterization of Magnesium Substituted Aluminophosphate Molecular Sieves with AEL Structure

MAPO-11 molecular sieves were synthesized by hydrothermal methods. The influence of precursor of magnesium, Mg/Al ratio, synthesis temperature, synthesis time and the type of template on the formation and properties of MAPO-11 molecular sieves was examined. The samples were characterized by the techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric/differential thermogravimetric analysis (TG-DGA), etc. The results show that the shape and size of crystal were influenced by the precursor of Mg, the Mg/Al ratio and the type of template, and the TG-DGA analysis shows that MAPO-11 molecular sieves as-synthesized have poor thermal stability.

MOLECULAR DESIGN OF NEW KINDS OF AUXETIC POLYMERS AND NETWORKS

Three new kinds of molecular networks are designed and predicted to exhibit negative Poisson ratios. Molecular mechanics calculations on these networks show that the magnitude of Poisson ratios depends on the relative flexibility of beam and arm structures. Several new kinds of auxetic polymers, whose successful synthesis should be easier than that of the corresponding auxetic networks, are then proposed. It is found that the kabob-like polymers with auxegens lying vertically on the main chain can acquire auxeticity while those with auxegens lying horizontally on the main chain cannot. Besides, a half kabob-like or pseudo-ladder polymer with auxegens linked at the intersection of the beam and the arm does show auxeticity when adopting constrictive conformers. It is, however, worthwhile noting that the origins of auxeticity still await and strongly deserve further experimental and theoretical investigations.

Carbon isotopic fractionation during vaporization of low molecular weight hydrocarbons(C6–C12)

Three series of laboratory vaporization experiments were conducted to investigate the carbon isotope fractionation of low molecular weight hydrocarbons（LMWHs）during their progressive vaporization.In addition to the analysis of a synthetic oil mixture,individual compounds were also studied either as pure single phases or mixed with soil.This allowed influences of mixing effects and diffusion though soil on the fractionation to be elucidated.The LMWHs volatilized in two broad behavior patterns that depended on their molecular weight and boiling point.Vaporization significantly enriched the ^13C present in the remaining components of the C6–C9 fraction,indicating that the vaporization is mainly kinetically controlled;the observed variations could be described with a Rayleigh fractionation model.In contrast,the heavier compounds（n-C10–n-C12）showed less mass loss and almost no significant isotopic fractionation during vaporization,indicating that the isotope characteristics remained sufficiently constant for these hydrocarbons to be used to identify the source of an oil sample,e.g.,the specific oil field or the origin of a spill.Furthermore,comparative studies suggested that matrix effects should be considered when the carbon isotope ratios of hydrocarbons are applied in the field.

High-precision spectroscopy of hydrogen molecular ions

In this paper, we overview recent advances in high-precision structure calculations of the hydrogen molecular ions （H2＋ and HD＋）, including nonrelativistic energy eigenvalues and relativistic and quantum electrodynamic corrections. In combination with high-precision measurements, it is feasible to precisely determine a molecular-based value of the proton- to-electron mass ratio. An experimental scheme is presented for measuring the rovibrational transition frequency （v,L） ： （0, 0） → （6,1） in HD＋, which is currently underway at the Wuhan Institute of Physics and Mathematics.

Investigation of Self-Diffusion and Structure in Calcium Aluminosilicate Slags by Molecular Dynamics Simulation

Molecular dynamics simulation is applied to investigate the mechanism and variation of self-diffusion in calcium aluminosilicate slags. The self-diffusion coefficients are calculated for eleven slag compositions with varying Al2O3/SiO2 ratios at a fixed CaO content. In practice, the results of the study are relevant to the significant changes in transport phenomenon caused by the changes in chemical composition during continuous casting of steels containing high amounts of dissolved aluminum. The cooperative movement between O atoms and network formers is discussed since [AlO4] and [SiO4] tetrahedra are the elementary structural units in the CaO-Al2O3-SiO2 (CAS) slag system. The diffusivities for four atomic types are affected by the degree of polymerization (DOP) of slag network characterized by the proportions of non-bridging oxygen (NBO) and Qn species in the system. On the other hand, a sudden increase in 5-coordinated Al as network modifiers in high alumina regions slightly increases the self-diffusion coefficient for Al. As another structural defect, oxygen tricluster plays an important role in the behavior of self-diffusion for O atoms, while the diffusivity for Ca is deeply influenced by its bonding and coordinating conditions.

PEG辅助合成片层结构钛硅分子筛催化氧化脱硫性能研究

以正硅酸乙酯为硅源、钛酸四丁酯为钛源、四丙基氢氧化铵为模板剂,采用聚乙二醇作为结构导向剂制备了片层结构钛硅分子筛,进行了表征和分析。结果表明:聚乙二醇辅助合成的钛硅分子筛(PTS)具有明显的片层结构、较高的比表面积和多级孔道结构;以1 000 mg/L噻吩-正辛烷为模拟油、H_(2)O_(2)为氧化剂进行脱硫性能实验,在相同脱硫时间内PTS-30(硅钛比为30)对噻吩脱除性能较传统钛硅分子筛提高近10%,循环7次后PTS-30分子筛脱硫性能仍保持60.2%。

分子印迹双发射比率荧光传感器的构建及其对微囊藻毒素的灵敏检测

本文以水体中的微囊藻毒素(MCs)为研究对象,通过制备硼掺杂碳量子点(B-CDs)和氮掺杂碳量子点(N-CDs),以二甲双胍为虚拟模板进行分子印迹,构建了一种检测水体中MCs含量的双发射比率荧光传感器。二甲双胍和常见的MCs(MC-LR,-RR,-YR)具有同样的胍基,通过印迹洗脱,可在SiO_(2)微球表面形成与MCs相类似的空腔结构。当溶液中存在MCs时,所制备分子印迹聚合物中的B-CDs荧光会对MCs产生响应,出现较为明显的荧光猝灭现象,而N-CDs不发生荧光猝灭,因此,以B-CDs荧光作为目标敏感信号,N-CDs荧光作为参比信号,从而实现MCs的比率荧光分析。实验结果表明,所构建的传感器对MCs有较好的选择性和较高的灵敏度,MCs浓度在0.5~150μg/L之间与荧光信号存在线性关系,其线性方程为I=0.00375c+1.03019,相关系数R2为0.9870,检测限为0.025μg/L。所建立方法对实际样品中MCs检测具有很好的应用前景。

大气多环芳烃的浓度水平、来源与健康风险评价综述

多环芳烃(PAHs)主要源于有机材料的不完全燃烧,具有生物蓄积性和毒性(致癌、致畸形和致突变),是一类持久性有毒物质。本文综述了大气PAHs的分类、排放特征、时空分布特征、来源解析和健康风险评价,根据不同相对分子质量、存在形式、化学结构进行PAHs分类。指出了PAHs浓度呈现季节性变化,变化趋势由高到低为:冬季、春季、秋季和夏季。比较了分子诊断比率(DRs)和受体模型,包括主成分分析(PCA)、化学质量平衡模型(CMB)、正矩阵分解(PMF)和多变量受体模型(Unmix)等多种PAHs源解析方法的优缺点。来源解析表明:DRs和PCA是应用最广泛的方法,但是其来源解析结果的准确性受到诸多因素的影响;PMF和Unmix相结合来解析PAHs来源,能仅根据受体部位的测量浓度来分配源,提供了PAHs源贡献的时间序列并且弥补了需要人为解读的局限性。文中展示了如何利用终身癌症风险增量(ILCR)模型将PAHs的来源分配用于评估健康风险,并在此过程中,确定了影响ILCR准确性的关键因素。以期为进一步开展大气PAHs污染相关研究提供参考。

ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究

通过水热法成功合成了一系列宽硅铝比(50、100、150、300、500、800、1500、3000)的ZSM-5分子筛,旨在研究其对涂装行业典型挥发性有机物(volatile organic compounds,VOCs)的吸附规律。同时,结合分子筛表面的酸性位点,以解析硅铝比对分子筛吸附性能的影响机制。实验结果表明,丙酮的吸附能力主要受自身极性、支链结构和分子筛表面酸位点的影响。而乙酸丁酯、苯乙烯、对二甲苯、苯、甲苯的吸附性能会同时受到自身的分子量、分子直径、极性、分子结构和官能团的影响,分子量和分子直径大、极性强且具有支链结构的VOCs更容易被ZSM-5分子筛吸附。这6种VOCs中,ZSM-5分子筛对丙酮的吸附效果最好,硅铝比对其吸附性能的影响也最大。这是因为丙酮比其他VOCs更容易吸附在Lewis酸位点上,硅铝比的改变会影响酸位点的数量。低硅铝比的分子筛由于具有较多的酸位点,更适用于丙酮的吸附。

500 kA铝电解槽节能降耗技术研究

浅析了铝电解槽能耗降低途径,综合考虑影响铝电解能耗的多种因素,在500 kA铝电解槽上开展了工艺优化试验,通过控制系统参数进准设置,Al_(2)O_(3)浓度、铝水平、分子比、过热度等工艺技术条件优化,使控制系统参数与铝电解槽技术条件高度匹配,实现铝电解槽电流效率提升、平均电压降低、铝液综合交流电耗大幅降低。

低硅铝比X型分子筛制备技术的开发

研究了低硅铝比X型(LSX)分子筛的合成体系和控制方法,探究了引入功能性物质制备高纯度、可调晶簇尺寸的LSX分子筛的可行性,通过优化分子筛水热反应配方和条件确定了制备LSX分子筛的技术方案并初步考察了晶簇尺寸与活性的关联性,进而采用工业原料实现了高品质LSX分子筛的合成。实验结果表明,在钾-钠双元体系中借助低温老化—高温晶化两段法可制备LSX分子筛;老化温度/时间、晶化温度/时间、硅铝比、碱硅比、水碱比及钠钾比能显著影响分子筛的合成过程;向反应体系中引入适当功能性物质可制备出结晶度高、含杂晶量少、活性佳、平均晶簇尺寸在1~4μm可调的LSX分子筛;由此能优化得到适合分子筛生产的长、短流程两套技术方案,进一步明确了上述手段具有保证本征活性不变,通过减小晶簇尺寸改善吸附剂传质系数的操作可能性;使用工业原料制备出了合格的LSX分子筛,放大合成的产品仍满足制氧吸附剂要求。

牵伸倍数对PE-UHMW膜材料性能的影响

高性能纤维增强树脂基复合材料的发展促进了防弹装备的发展,在面对高能杀伤武器威胁加剧和单兵携行负荷增加的情况下,防护装备高防护、轻量化的需求日益迫切,超高分子量聚乙烯(PE-UHMW)膜材料的出现,有助于满足轻质高防的需求。PE-UHMW条带作为PE-UHMW膜材料的最小组成,对膜材料性能的影响决定防弹装备的性能。为探究不同牵伸倍数对膜材料性能的影响,选取由不同牵伸倍数条带制备的膜材料开展理化特性、力学性能和防弹性能研究。测试分析发现,PE-UHMW膜材料在分子量、结晶度、取向度等理化特性的不同使层压得到的复合材料力学性能有所差异,进而在不同弹击条件下防弹性能呈现出差异化特点。由高倍牵伸条带制备的膜材料分子量达到5 658 000 g/mol,由其制备的复合材料具有更加优异的力学性能,弯曲强度为102.12 MPa,弯曲弹性模量为23.30GPa,剪切强度为8.60 MPa,经过层压制备的8 kg/m^(2)面密度靶板在常温条件下防1.1 g标准模拟破片V50值达到了804.50 m/s,51式7.62 mm手枪弹弹着点弹痕高度为13.20 mm。在树脂体系与加工工艺一致的情况下,由高牵伸倍数PE-UHMW条带制备的PE-UHMW膜材料在力学和防弹性能方面具有明显优势,具备在个体防护领域的应用潜力。

一种MTW结构分子筛的合成及其二甲苯异构化反应性能

采用类似五元环中间体结构的烷基吡咯烷为模板剂,通过动态水热法在不同碱度比和硅铝比条件下合成了一种具有MTW拓扑结构的分子筛(LMTW),通过XRD、N_(2)吸附-脱附、SEM、Py-FTIR和电子晶体学等方法对分子筛的结构进行表征。以该分子筛为酸性组分,负载铂制备了转化型二甲苯异构化双功能催化剂(Pt/LMTW),使用微型活塞流反应器对催化剂的反应性能进行评价,并与Pt/REI-430催化剂的性能进行比较。实验结果表明,合成的LMTW分子筛具有和MTW分子筛一致的特征峰及相似的晶胞参数,合成过程中的碱度比和硅铝比会影响分子筛的孔道结构、比表面积及酸性等。与Pt/REI-430催化剂相比,制备的Pt/LMTW催化剂用于二甲苯异构化反应具有优异的性能。

不同硅铝比Beta分子筛水蒸气动态吸附性能研究

硅铝沸石分子筛在吸附领域应用广泛,其亲、疏水性能对吸附性能影响较大,但硅铝沸石分子筛在不同条件下的水蒸气动态吸附性能尚不明确。采用不同硅铝比(n(SiO_(2))/n(Al_(2)O_(3))=30、135或679)的Beta分子筛(Beta-30、Beta-135和Beta-679)作为研究对象,先采用XRD、FT-IR和TG等对其进行了表征,然后在不同温度和相对湿度(HR)下分别进行了Beta-30、Beta-135和Beta-679的水蒸气吸附容量和相应动力学分析。结果表明,当温度为25℃或35℃、H_R小于80%时,Beta-679的吸附容量最低。当温度为15℃、HR为5%~10%时,Beta-679的平衡速率最快。当温度为15℃、H_R为50%~70%时,Beta-30、Beta-135和Beta-679的平衡速率表现出较大区别(Beta-135的平衡速率远小于Beta-30和Beta-679的平衡速率)。