CL-20热分解反应机理的ReaxFF分子动力学模拟

为探究固相CL-20热分解反应机理,本文采用反应分子动力学ReaxFF MD模拟研究了含有128个CL-20分子的超胞模型在800–3000 K温度下的热分解过程。借助作者所在课题组研发的反应分析及可视化工具VARxMD得到了热分解过程中多种反应中间物和较为全面的反应路径。氮氧化物是CL-20初始分解的主要中间产物,其中NO₂是数量最多的初始分解产物,观察到的中间物NO₃的生成量仅次于NO₂。统计CL-20初始分解的所有反应后发现,在所有考察温度下CL-20初始分解路径主要是N―NO₂断裂反应和C―N键断裂引起开环的单分子反应路径。N―NO₂断裂反应数量在高温下显著增多,而C―N键断裂引起的开环反应数量随温度升高变化不大。在低温热分解模拟中还观察到CL-20初始分解阶段生成的NO₂会发生双分子反应—从CL-20分子中夺氧生成NO₃。对CL-20热分解过程中环结构演化进行分析后发现,CL-20分解的早期反应中间物主要为具有3元或2元稠环结构的吡嗪衍生物,随后它们会分解形成单环吡嗪。吡嗪六元环结构在热分解过程中非常稳定,这一模拟结果支持Py-GC/MS实验中提出吡嗪存在的结论。CL-20中的咪唑五元环结构相对不稳定,在热分解过程中会发生开环分解而较早消失。由ReaxFF MD模拟得到的3000 K高温热分解产物N₂,H₂O,CO₂和H₂的数量与爆轰实验的测量结果定量吻合。本文获得的对CL-20热分解机理的认识表明ReaxFF MD结合VARxMD有可能为深入了解热刺激下含能材料复杂化学过程提供一种有前景的方法。     

Detailed Temperature-dependent Study of n-Heptane Pyrolysis at High Temperature

n-Heptane is the most important straight chain paraffin in the fossil-fuel industry. In this work, pyrolysis behavior of n-heptane at high temperature is investigated by a se-ries of ReaxFF based reactive molecular dynamics simulations. Temperature effects on then-heptane pyrolysis and related products distributions have been detailedly analyzed. The simulation results indicate that the temperature effect is characterized in stages. High tem-perature can accelerate the decomposition of n-heptane, but the influence becomes small after it reaches a certain level. According to the different reaction behaviors, pyrolysis of n-heptane could be divided into three stages. The variation trends of the mass fraction evolu-tion of ethylene (C₂H₄), C3, and C4 calculated from reactive molecular dynamics simulations are in good agreement with the previous experimental results. The apparent activation en-ergy extracted from the first-order kinetic analysis is 53.96 kcal/mol and a pre-exponential factor is 55.34×10¹³ s^-1, which is reasonably consistent with the experimental results.     

RDX及其衍生物高温热解的反应分子动力学模拟

本文采用ReaxFF反应分子动力学方法,研究了RDX及其衍生物晶体在高温条件下(2000、2500和3000 K)的热分解机理以及主要产物随时间的变化情况。结果表明:RDX及其衍生物晶体热解的第一步反应均为N―NO_2键断裂生成NO_2分子,随后反应由于六元环上和侧链基团的不同导致侧链脱除或开环反应的顺序不同。在这四种单胞体系热解中,NO_2和NO分子为共同的中间产物,形成之后迅速发生次级反应并最终生成N_2。各体系热解终产物一致,均为N_2、H_2O和CO_2,其中N_2分子数最多,大于20个。由于原始分子结构和组成中C/N比、H/O比的不同,各体系热解后H_2O和CO_2分子数目相差较大。不同温度下,各单胞体系热分解生成的最大含碳团簇中C原子数均较小。在进一步超胞体系的模拟中,RDX和RDX-D2体系生成的含碳团簇中C原子数分别达到约30和16个,远高于单胞模拟,且受温度影响较大;而RDX-D1和RDX-D3单胞或超胞模拟结果相近,均未生成含碳团簇,仅存在小分子含碳碎片。因此,初始分子的结构和元素比对含碳团簇的生成有明显影响。     

印刷电路板中环氧树脂热解的ReaxFF反应动力学模拟

采用ReaxFF动力学方法模拟了非交联固化环氧树脂在不同温度和升温速率下的热解特性. 结果表明, 含N和含O桥键的断裂是热解的引发反应. 观察到H₂O的4种主要的生成途径, 而这些反应途径都涉及到含羟基的前驱体. 当反应温度较低时, H₂O为热解的主要产物. 而在高温条件下, 热解的主要产物为H₂, 它主要为分子内/分子间脱氢反应和氢自由基的夺氢反应的产物; 高温同时促进了含石墨烯结构且分子量较大的碳团簇的形成. 除此之外, 还观察到了CH₄, HCN, NH₃和CO等小分子产物. 本文用ReaxFF动力学方法模拟所得的气体产物以及含类似石墨烯结构的碳团簇与实际实验结果一致, 说明ReaxFF动力学方法能为从分子水平上研究有机物高温热解反应提供了一种有效的途径.     

水分子对α相CL-20热分解机理影响的分子动力学研究

研究六硝基六氮杂异伍兹烷(CL-20)晶体不同晶型在不同温度下的反应机理, 对于深入认识含能材料在极端条件下的冲击起爆、冲击点火和爆轰过程等具有重要意义. 基于反应力场, 研究水分子在纯α相CL-20及其水合物的晶体结构中数量随时间的变换, 分析水分子对两种体系的初始分解和第二阶段的分解路径的影响. 计算结果表明: CL-20 分子的初始分解路径与水分子无关, 第二阶段的分解反应与水分子有关. 在低温(T<1500 K)下, 水分子对两种体系没有影响, 二者的初始分解路径均为N-NO₂键生成NO₂自由基; 在1500 K≤T≤2500 K时, 水分子作为反应物或与NO₂、、OH自由基等组成催化体系, 生成O₂、H₂O₂等产物, 加速水合物体系在高温下的第二阶段反应, 使得高温下水合物体系的化学反应速率和反应生成的NO₂自由基的数量比纯CL-20体系的化学反应速率和反应生成的NO₂自由基的数量大; 在T>2500 K时, 水分子的催化反应抑制CL-20初始分解反应, 使得在3000 K时纯CL-20体系的反应速率大于水合物体系中CL-20的反应速率.     

分子动力学模拟在聚合物热解中的应用

分子动力学模拟作为分子模拟的重要分支已经在化学、化工、材料、生物等领域受到了广泛的关注。介绍了分子动力学模拟的基本原理,阐述了分子动力学模拟在高分子聚合物热解反应机理研究中的应用。实例表明:在研究物质化学反应机理方面,分子动力学模拟是一种有效的研究手段。     

铝粉粒度对高氯酸铵热分解动力学的影响

采用热重-差示扫描量热(TG-DSC)联合技术研究了10.7 μm, 2.6 μm和40 nm铝粉对高氯酸铵(AP)热分解的影响. 结果表明, 铝粉的加入对AP的低温放热峰有抑制作用, 对高温放热分解反应有促进作用, 并且随铝含量的增加和铝粒径的减小这种作用更强烈. 采用多元非线性拟合技术对不同升温速率下TG-DSC实验数据进行拟合, 结果表明, 质量分数为40%的不同粒径铝粉的加入对AP的热分解三阶段(A→B→C→D)反应模型无影响, 但反应机理函数发生了改变. 纯AP, AP/Al(10.7 μm), AP/Al(2.6 μm)及AP/Al(40 nm)的反应机理函数组合分别为C1/D1/D1, C1/D1/D3, C1/D1/D4和C1/D1/F2.     

热辅助存储磁盘硅掺杂非晶碳薄膜氧化的ReaxFF反应力场分子动力学模拟

Heat-assisted magnetic recording (HAMR) is one of the promising ways to extend the magnetic recording area density to 1 Tb·in^-2 in hard disk drives (HDDs).High temperature induced by laser heating can cause carbon overcoat (COC) oxidation.Reactive molecular dynamics (MD) simulations are performed to investigate the oxidation process of silicon-doped amorphous carbon (a-C:Si) films for HAMR application.The atomic details of the structure evolution and oxidation process are investigated, and, the oxidation mechanism of the a-C:Si film is clarified.The effect of the duration of laser irradiation on the oxidation of the a-C:Si film is investigated.The oxidation occurs during heating and the beginning of cooling process.Both volume expansion during heating process and cluster of carbon atoms during cooling process increase the rate of sp² carbon.Because of the decrease in the amount of unsaturated silicon atoms and low diffusion coefficient of atomic oxygen, the oxidation rate of the a-C:Si film decreases with laser irradiation cycles.The molecular oxygen is the oxidant due to surface defect of a-C:Si film.The atomic strains break the O-O bonds in Si-O-O-Si linkages and rearrange the surface oxide layers, and process the oxidation of the a-C:Si film.     

聚氨酯胶粘剂的热分解动力学研究

采用热分析技术考察了通用型聚氨酯胶粘剂在空气中的热解过程, 并通过TG方法和动力学方法研究了各步反应的活化能E、指前因子A等动力学参数. 通过等失重转化率法校验了两种方法所获得的E和A值. 结果表明, 聚氨酯胶粘剂有三个主要降解阶段, 第一降解阶段的活化能为144.31-148.35 kJ·mol^-1, 第二个降解阶段的活化能为196.96-204.26 kJ·mol^-1, 第三个降解阶段的活化能为202.97-205.27 kJ·mol^-1; 热降解过程为一级反应, 随着失重百分率的增大, 热分解反应活化能增大. 此外, 聚氨酯胶粘剂具有较高的热稳定性, 预测其在35 ℃的空气中失重5%时的热老化寿命为10年.     

TNT高温热解及含碳团簇形成的反应分子动力学模拟

ReaxFF-MD模拟三硝基甲苯(TNT)高温热解显示增加了伦敦耗散力项(E_lg)的ReaxFF/lg 势函数在含能材料平衡密度计算方面具有优越性. 产物识别分析得出TNT热解的主要产物为NO₂、NO、H₂O、N₂、CO₂、CO、OH以及HONO,且最终产物为H₂O、N₂和CO₂. 使用ReaxFF势函数模拟同样过程进行比较性分析显示,在主要产物和最终产物方面与ReaxFF/lg 作用结果具有一致性,但在化学反应动力学方面表现出一些差异. ortho-NO₂键断裂和C―NO₂→C―ONO重排布-断裂形成NO₂和NO是TNT热解的主要初级反应,且前者产生速率大于后者,NO₂和NO形成后很快参与次级反应并最终形成N₂. 高温热解中形成OH等小分子会促进H₂O的形成. 环上基团相互反应或直接脱落后,主环间C―C键才发生断裂,但温度升高会加快主环断裂,并进一步分解形成CO₂,这也是高温条件下CO₂分布产生波动的一个重要原因. 并且当晶胞中的TNT分子几乎完全分解时,系统的势能开始明显衰减. 与温度相比,密度对热解中最大含碳团簇形成的影响更明显. 并且,模拟结果显示,在TNT完全分解前已经出现含碳中间体的聚合现象. 此项工作表明使用ReaxFF/lg 反应力场研究TNT高温热解可以提供具体的动力学和化学方面的信息,并有助于理解含能材料的爆轰问题并可进行安全评估.     

单斜仲钨酸铵热分解的热化学测定

The heat of the thermal decomposition of monoclini c ammonium paratungstate, (NH4)10H2W12O42•4H2O, was measured in a HT-1000 microcalorimeter using three-step calorimetry and suitable thermochemical cycle. The standard enthalpy of the thermal decomposition reaction at 298.15 K and the standard enthalpy of formation at 298.15 K for monoclinic ammonium paratung-state were obtained to be (430.1± 10.2) kJ•mol－ 1 and－ (13 423.7±14.8) kJ•mol－ 1, respectively.     

六氟乙烷的热分解特性

采用管式炉研究了950~1100 ℃温度区间C2F6的分解特性, 并研究了C2F6的初始浓度、反应温度、停留时间对C2F6分解率的影响. 实验结果表明, C2F6初始浓度越低、温度越高、反应时间越长, C2F6分解率就越高. 同时, 热解反应的反应级数应该介于0和1之间. 在温度为1100 ℃, C2F6初始浓度为223.21 μmol/L, 停留时间为2 s时, C2F6分解率高达90%. 根据Arrhenius方程计算, 在950~1100 ℃, C2F6热分解反应的活化能(Ea)为313.2 kJ/mol, 频率因子(A)为8.8×1011 s-1.     

ReaxFF MD局部区域反应追踪与物理性质可视化分析

Recently, the application of ReaxFF based reactive molecular dynamics simulation (ReaxFF MD) in complex processes of pyrolysis, oxidation and catalysis has attracted considerable attention. The analysis of the simulation results of these processes is challenging owing to the complex chemical reactions involved, coupled with their dynamic physical properties. VARxMD is a leading tool for the chemical reaction analysis and visualization of ReaxFF MD simulations, which allows the automated analysis of reaction sites to get overall reaction lists, evolution trends of reactants and products, and reaction networks of specified reactants and products. The visualization of the reaction details and dynamic evolution profiles are readily available for each reactant and product. Additionally, the detailed reaction sites of bond breaking and formation are available in 2D chemical structure diagrams and 3D structure views; for specified reactions, they are categorized on the basis of the chemical structures of the bonding sites or function groups in the reacting species. However, the current VARxMD code mainly focuses on global chemical reaction information in the simulation system of the ReaxFF MD, and is incapable of locally tracking the chemical reaction and physical properties in a 3D picked zone. This work extends the VARxMD from global analysis to a focused 3D zone picked interactively from the 3D visualization modules of VARxMD, as well as physical property analysis to complement reaction analysis. The analysis of reactions and physical properties can be implemented in three steps: picking and drawing a 3D zone, identifying molecules in the picked zone, and analyzing the reactions and physical properties of the picked molecules. A 3D zone can be picked by specifying the geometric parameters or drawing on a screen using a mouse. The picking of a cuboid or sphere was implemented using the VTK 3D view libraries by specifying geometric parameters. The interactive 3D zone picking was implemented using a combination of observer and command patterns in the VTK visualization paradigm. The chemical reaction tracking and dynamic radial distribution function (RDF) of the 3D picked zone was efficiently implemented by inheriting data obtained from the global analysis of VARxMD. The reaction tracking between coal particles in coal pyrolysis simulation and dynamic structure characterization of carbon rich cluster formation in the thermal decomposition of an energetic material are presented as application examples. The obtained detailed reactions between the coal particles and comparison of the reaction between the locally and globally picked areas in the cuboid are helpful in understanding the role of micro pores in coal particles. The carbon to carbon RDF analysis and comparison of the spherical region picked for the layered molecular clusters in the pyrolysis system of the TNT crystal model with the standard RDF of the 5-layer graphene demonstrate the extended VARxMD as a chemical structure characteristic tool for detecting the dynamic formation profile of carbon rich clusters in the pyrolysis of TNT. The extended capability of VARxMD for a 3D picked zone of a ReaxFF MD simulation system can be useful for interfacial reaction analysis in a catalysis system, hot spot formation analysis in the detonation of energetic material systems, and particularly the pyrolysis or oxidation processes of coal, biomass, polymers, hydrocarbon fuels, and energetic materials.     

单斜仲钨酸铵热分解的热化学测定

在钨的冶炼过程中,仲钨酸铵是必须的中间原料 .从溶液中结晶仲钨酸铵时,根据结晶条件的不同,可以得到不同类型的结晶 [1].一般在较低的温度时（低于 323 K）,得到三斜仲钨酸铵 (NH4)10H2W12O42· 10H2O,在较高温时（高于 323 K）,得单斜仲钨酸铵 (NH4)10H2W12O42· 4H2O.工业生产中,单斜仲钨酸铵是常见的产品 .仲钨酸铵的质量直接决定钨粉的质量,因此仲钨酸铵热力学性质对于控制其结晶条件及结晶的热分解条件具有重要的指导意义 .但迄今,很少有关于单斜仲钨酸铵的热力学性质的报导 .本文用双子型热导式微量热量计,根据单斜…     

酚醛树酯的热解动力学模型

建立了一种利用热重峰值分析进行酚醛树酯热解动力学研究的方法, 这种方法利用热重谱峰上几个特征点的数据来确定动力学参数. 根据酚醛树酯热解DTG曲线的特点, 把酚醛树酯的热解过程分解成三个阶段, 用峰值分析法对每个反应阶段分别建模, 通过三个反应阶段的叠加得到了一个酚醛树酯分阶段热解动力学模型, 该模型能够很好地描述酚醛树酯的热解过程.     

硅烷热分解制备硅原子簇

当前，半导体硅原子簇的物理与化学性能已成为人们广泛研究的热点[1]．尽管近几年来硅原子簇研究取得很大进展，但对于大于10个原子的硅原子簇的实验及理论研究尚很少见[2]．目前，均采用在超高真空系统中，利用脉冲激光蒸发硅棒获得硅原子簇，然后进行分析．检测及化学反应研究，还不能离开真空系统．为此，发展一种能够制备可观量的、在大气中稳定的原子簇的方法很有必要．我们利用硅烷热分解的化学方法，制备硅原子簇工艺，如图1所示．采用MO丝加热，以Ar气稀释SM。气体，为防止气管喷嘴在反应中被产物堵塞，使用了Cap2保护，控制温度…     

Thermal decomposition studies of catalysed double base propellants

To understand the rote of lead salts of organic acids in the combustion of double base rocket propellants, thermal decomposition behaviour of propellants was studied bydta andtg methods. Catalysed propellants decomposed at lower temperatures than the control. Percent thermal decomposition of propellants containing lead salts was also higher. Rate constants were higher and energy of activation was lower for catalysed propellants. Results obtained suggest that condensed phase reactions may be the site for the action of lead salts in the combustion of double base propellants     

硫酸铝钾热分解反应动力学模型

近年来,在热分析动力学研究领域内,已有许多动力学模式及相应数据处理方法来描述固相反应的最可能机理,如：aRCHAR微分法[1]Coats-Redfe积分法[2]相结合的方法和等温过程与非等过程相结合的方法[3]等。而最近Dollimore等人[4]提出了利用 TA曲线的特征来确定动力学模型的方法,从而避免了对 f(a)和 g(a)逐一尝试的麻烦。本文就是用该法来研究硫酸铝钾的热分解动力学。硫酸铝钾热分解过程虽然已有人研究[5],但其动力学则未见文献报道。1 实验部分 实验工作在美国PE公司TGA７热分析仪上完成,反应气氛为氮气,流速为40mL·min-1 ,…     

热分析-傅里叶变换红外光谱-气相色谱-质谱联用测定葡萄糖的热分解产物

应用热分析-傅里叶变换红外光谱-气相色谱-质谱联用测定葡萄糖的热分解产物。葡萄糖样品在同步热分析条件下,分别在氮气和氮氧混合气氛围中进行热解,同时进行红外扫描,根据样品的热重曲线和红外谱图进行判定和选择GC-MS温度点,裂解产物进入GC-MS进行分离和鉴定。结果表明:葡萄糖在220℃,300℃,350℃和470℃下的热分解产物中共检出44种化合物;葡萄糖在高温下的热裂解产物中共检出76种化合物。分析结果对葡萄糖在不同温度下的应用有较好的理论指导。     

Molecular Dynamics Simulation of Methane Hydrate Decomposition in the Presence of Alcohol Additives

The decomposition process of methane hydrate in pure water and methanol aqueous solution was studied by molecular dynamics simulation. The effects of temperature and pressure on hydrate structure and decomposition rate are discussed. The results show that decreasing pressure and increasing temperature can significantly enhance the decomposition rate of hydrate. After adding a small amount of methanol molecules, bubbles with a diameter of about 2 nm are formed, and the methanol molecules are mainly distributed at the gas-liquid interface, which greatly accelerates the decomposition rate and gas-liquid separation efficiency. The radial distribution function and sequence parameter analysis show that the water molecules of the undecomposed hydrate with ordered ice-like configuration at a temperature of 275 K evolve gradually into a long-range disordered liquid structure in the dynamic relaxation process. It was found that at temperatures above 280 K and pressures between 10 atm and 100 atm, the pressure has no significant effect on hydrate decomposition rate, but when the pressure is reduced to 1 atm, the decomposition rate increases sharply. These findings provided a theoretical insight for the industrial exploitation of hydrates.