冲击压缩下甲烷-空气混合气体状态参数实验研究

 为研究强冲击状态下混入少量空气的甲烷气体的冲击状态参数,利用二级轻气炮加载技术,使加速到5 km/s的钨合金飞片撞击封装有常态下空气混入量依次为零（纯甲烷气体）、1%、5%、10%的甲烷-空气混合气体铝靶。采用六通道瞬态光学高温计记录冲击压缩气体的光辐射历程曲线,得到了相同初始条件下4种不同比例混合气体的冲击状态参数。结果表明,在强冲击压缩下,混合气体的冲击温度随着空气混入比例的增大而增高,冲击波后混合气体存在非平衡辐射过程。采用Saha电离平衡方程,对空气混入量为10%的混合气体的电离度进行了估算。结果表明,常态下空气含量C_air≤10%的甲烷 空气混合气体具有电探针保护能力。     

O3对甲烷／空气着火过程的影响

本文基于零维均质着火系统研究了非平衡等离子中臭氧（O3）对甲烷／空气着火过程的影响,并通过化学反应路径分析揭示了O3促进甲烷／空气着火的化学反应机理。研究结果表明,O3促进甲烷／空气着火手要是通过化学反应动力学效应来实现的,热效应的影响十分有限。在不添加O3时,甲基的氧化速率缓慢,从而导致甲烷／空气不易着火;在添加O3...     

2-氢七氟丙烷在不同温度下的热分解

采用快速热解法以及傅里叶变换红外光谱(FTIR)和气相色谱/质谱(GC/MS)检测技术,研究了2-氢七氟丙烷在驻留时间为30 s,反应温度分别为400, 500, 600, 700和800 ℃时的热分解过程。结果发现：反应温度对2-氢七氟丙烷的热分解有明显的影响,2-氢七氟丙烷在400,500和600 ℃时是稳定的,在700 ℃时明显地开始分解,800 ℃时发生了强烈的分解。与此同时,在800 ℃时,在反应器的管壁上观察到了大量的焦炭,并在热分解产物中发现了1,2-二(三氟甲基)全氟茚满、全氟(1-亚乙基茚满) 和八氟化萘等三种环状化合物,这表明2-氢七氟丙烷在高温热分解过程中并不只是发生了简单的分解,环化和聚合过程也是会发生的。     

甲烷-空气最小点火能量预测理论模型

 最小点火能是可燃气体危险性辨识的重要参数之一。为从理论上得到混合气体的最小点火能,建立了可燃气体火花点火的物理模型,给出了通过数值模拟得到的可燃气体最小点火能量的预测方法,采用该方法得到了甲烷-空气混合气火花点火的临界温度及最小点火能量。结果表明：甲烷-空气混合气的最小点火能量与浓度呈U型关系,浓度为8.5%的预混气的最小点火能量计算值为0.39 mJ,与实验值0.4 mJ吻合较好。     

氢气比例和点火能量对CH4-H2混合气体爆炸强度影响的实验研究

在20 L标准球形爆炸罐内开展了当量比为1的甲烷-氢气-空气混合气体爆炸实验,通过改变点火能量和氢气体积分数,探讨点火能量和气体比例对其爆炸压力和爆炸强度的影响。研究发现:氢气比例越高,爆炸冲击波传播速度越快,点火能对冲击波传播速度的影响相对较小;点火能量的提高对峰值超压有增强作用,氢气比例低时,此增强作用较显著,氢气比例高时,此增强作用较弱;点火能量对爆炸强度指数KG的影响较小,而氢气比例对爆炸强度指数KG的影响十分明显,氢气比例低于50%时,氢气比例的增加对爆炸强度的增强作用较弱,氢气比例高于50%时,氢气的增加对爆炸强度的激励作用急剧增强。另外发现,相同当量比条件下,氢气的爆炸强度指数近似为甲烷爆炸强度指数的10倍。     

强激光场中氘团簇双重膨胀引发核聚变

在超强fs激光与氘团簇的相互作用中, 分析了可以引发核聚变的高能氘核产生的原因,提出了团簇双重膨胀的机制,计算了氘核动能及团簇解体的时间, 为选取合适的激光脉冲宽度参数提供参考. Considering the Coulomb explosion induced by the interaction of a deuterium cluster target with ultra intensity femtosecond laser,the causation which generate energetic deuterium nuclei for the fusion has been analyzed. The mechanism for the dual explosion of deuterium cluster is proposed, and hence the velocity of deuterium nuclei and the expansion time of deuterium ion clusters have been estimated.     

外电场下c-C4F8和C3F7CN分子福井函数与电负性研究

为了量化研究外电场对c-C4F8和C3F7CN气体化学稳定性和灭弧性能的影响,采用密度泛函B3LYP方法在6-311G*基组水平上计算了其福井函数、简缩福井函数和电负性.结果表明:c-C4F8内亲电、亲核反应位点均在F原子上,随着电场在-0.03a.u.至0.03a.u.范围内变化,碳环上关于电场方向对称的两组F原子的简缩福井函数变化一致,位于电场方向的两组F原子的简缩福井函数变化呈现互逆性;c-C4F8的电负性随着电场绝对值的增大而增强.C3F7CN内亲电、亲核反应位点均为5N、4C、12F,随着电场变化,5N、4C亲电反应活性增强,亲核反应活性减弱,12F亲电反应活性减弱,亲核反应活性增强;相比c-C4F8,C3F7CN电负性受电场大小和方向的影响,随着电场的变化而逐渐减弱.无外电场时,c-C4F8和C3F7CN的电负性分别为SF6的0.67倍和0.77倍.     

Trapping mechanism of superconductivity suppression induced by Pr substitution in the Ho1−xPrxBa2Cu3O7−δ system

Pr concentration dependence of the superconducting transition temperature T_c in the Ho_1−xPr_xBa₂Cu₃O_7−δ system is determined from measurements of DC electrical resistance. This dependence coincides with that for the parallely studied Y_1−xPr_xBa₂Cu₃O_7−δ reference system. Both systems have the same value of the critical concentration x_c=0.58, in accordance with nearly equal ionic radii of Ho³⁺ and Y³⁺ ions. It has been shown that the T_c(x) curve can be described with a single mechanism based on a decreasing number of sheet holes trapped by Pr^IV-ions, if one takes also into account that the number of these ions changes with x.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

电荷调控下Ti3C2O2和V2CO2吸附CH4的第一性原理计算

本文采用第一性原理计算首先研究了Ti3C2O2和V2CO2与CH4气体分子之间的相互作用,发现Ti3C2O2和V2CO2对CH4的吸附较弱属于物理吸附,不适宜用作探测CH4。在此基础上研究了电荷调控下CH4气体分子与Ti3C2O2和V2CO2之间的相互作用。结果表明：随着体系电荷态的增加,Ti3C2O2和V2CO2对CH4气体分子的吸附作用逐渐增加变为化学吸附。当体系电荷态大于或等于-2时,CH4气体分子在Ti3C2O2和V2CO2表面可以被有效捕获。撤去电荷后,Ti3C2O2、V2CO2与CH4气体分子之间的吸附恢复至物理吸附,CH4气体分子易脱附。因此,通过调控Ti3C2O2和V2CO2的电荷态,可以简单地实现CH4的捕获与释放。Ti3C2O2和V2CO2有望成为CH4探测或捕获材料。     

单源进液金属有机化学气相沉积法工作气压对YBCO薄膜制备的影响研究

基于金属有机化学气相沉积法(MOCVD),在沉积有Y2O3/YSZ/ CeO2( YYC)多层过渡层的Ni - W_at.5％金属基带上沉积YBa2Cu3O7-x(YBCO)超导薄膜.通过对单源进液系统的优化,使金属有机源连续稳定地输送到蒸发皿进行闪蒸.优化总气压并通入N2O气氛,以获得高质量的YBCO薄膜.在优化的温...     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.