关于判断反应自发方向的讨论

本文对在一定条件下,用标准吉布斯自由能变面△Ｇ~０、反应商（Ｑ_ｐ、 Ｑ_ｃ、 Ｑ~０）、焓变（△Ｈ）、电池电动势（Ｅ）代替吉布斯自由能变△Ｇ判断反应自发方向进行了讨论。     

聚钛碳硅烷的新合成法及其研究

从聚硅烷(PS)与钛酸丁酯。(Ti(OBu)_4)出发,不采用任何反应促进剂直接合成了含钛碳化硅纤维的先驱体聚钛碳硅烷(PTC)。在这一反应中,PS 首先裂解成含Si—C 骨架与Si—H 键的低分子聚硅烷(LPS)。然后,由LPS 中的Si—H 键与Ti(OBu)_4的反应以及LPS 的Si—Si 骨架裂解转化为Si—C 骨架的反应制得了PTC.本文对这种新合成法所涉及的反应过程进行了研究,并比较了新旧两法得到的PTC—1与PTC—Ⅱ的结构异同,报告了以新法制得的PTC—Ⅱ为先驱体得到的含钛碳化硅纤维的优良性能。     

聚苯乙炔的合成及其表征——用无水AlCl3和(Ph3P)2PdCl2二种催化剂

本文用无水AlCl_3和(Ph_3P)_2PdCl_2二种催化剂催化苯乙炔聚合,得到共轭聚合物聚苯乙炔(PPA)。对PPA 的微结构分析表明:用无水AlCl_3催化苯乙炔,得到顺-反式PPA;用(Ph_3P)_2PdCl_2催化苯乙炔得到反-顺式PPA.因此,作者认为用无水AlCl_3催化苯乙炔聚合时可能按络合催化机理反应;用(Ph_3P)_2PdCl_2催化苯乙炔聚合时可能按易位催化机理反应。     

C76、C78、C82、C84和C90的π电子磁化率

采用规范不变分子轨道方法,计算了Ｄ_２—Ｃ_（７６）、Ｃ_（２ｖ）￣－和Ｄ_３—Ｃ_（７８）、Ｃ_２—Ｃ_（８２）、Ｄ_２—和Ｄ_（２ｄ）—Ｃ_（８４）以及Ｃ_２—Ｃ_（９０）的л电子磁化率。其结果表明这些纯碳原子团簇分子具有较大的抗磁磁化率。反映出这些分子具有一定的芳香性及其л电子有较大的共有化运动程度。     

聚钛碳硅烷的结构与性能研究

通过聚碳硅烷与四丁氧基钛的反应。可以制得含钛碳化硅纤维的先驱体聚钛碳硅烷。反应物配比(Ti(OBu)_4)/PC 将直接影响产物的结构与性能。随这一比例的增加,聚钛碳硅烷的可纺性与熔点将有规律地变化。这可归因于以—Ti—O—为桥的交联结构和以—Ti(OBu)_3为侧基的悬挂结构的形成。本文研究了聚钛碳硅烷的结构与性能的关系,并以具有良好成丝性的PTC-0.02与PTC-0.04为先驱体,制得了含钛碳化硅纤维。     

碳化钨及其混合物的冲击 Hugoniot数据计算

计算了多孔碳化钨（初始密度分别为密实碳化钨密度的９５％、８５％、７５％和６５％）在不完全压实状态和完全压实状态下的Ｐ_１－Ｖ_１曲线和Ｃｓ－Ｕ１曲线以及碳化钨／碳、碳化钨／碳化硅混合物（碳化钨含量分别为３％,５％,１０％）的Ｐ_１－Ｖ_１曲线和Ｃ_ｓ－Ｕ_１曲线。     

一类随机差分方程的解序列的最优停止规则

设报酬序列{x_(?),(?),n≥0}满足随机差分方程x_(n+1)=x_n+a_n+b_nε_(n+1)(ε_1,ε_2,…为白噪声序列)。本文讨论了用有限情形{x_n,0≤n≤N}的Snell包逼近无限情形{x_n,n≥0)的Snell包的条件,得到了x_n=E(x_n|(?))((?)=σ{ε_0,ε_1,…,ε_n},ε_0=0)的Snell包r_n的分解形式和最优停时存在的条件。最后讨论了最优停止规则的迭代计算法,并得出了迭代过程在有限步停止的充分条件。     

化学非平衡尾迹流场的数值计算

高超音速化学非平衡尾迹流场的分析及计算是再入空气动力学的一个重要课题。本文采用轴线极限方程,成功地消除了控制方程在轴线上的奇性;采用二阶精度的中心差隐格式,求解了抛物化的Ｎ－Ｓ方程,得到了２０ｋｍ及６０ｋｍ再入时尾迹流场的数值解。计算结果表明,在远尾迹场,对电子数密度的主要影响是Ｏ_２的吸附反应。     

Cu(Ⅱ)大环希夫碱配合物的合成与表征

以邻苯二甲醛和邻苯二胺为原料,三水合硝酸铜为模板剂,用模板反应在无水乙醇中制备了一种新的固体配合物[CuL](NO_3)_2·6H_2O。通过元素分析、磁化率及摩尔电导测定、红外光谱和电子光谱分析、热重-差热分析等,确定了配合物的组成、立体结构与对称性,并对其电致变色机理进行了初步的探讨。     

冠脉搭桥术用 CO2 激光低能输出方法研究

弱ＣＯ_２激光能量的输出及控制是ＣＯ_２激光冠脉搭桥术的核心技术之一。本文介绍了一种利用普通医用ＣＯ_２激光器获得弱激光能量输出的技术与方法。该方法具有激光输出功率稳定,并可调、输出光斑上能量密度均匀,光斑大小可控的特点,它很好地满足了搭桥仪对激光输出参数的要求;该方法还可应用于其它弱ＣＯ_２激光医疗仪器中。文中对设计原理进行了分析,并给出了设计实例。     

气体化学反应速率的 DSMC 方法

为预报化学反应过程,应用ＤＳＭＣ方法研究了双原子分子的离解反应,讨论了高温情况下（Ｔ～Ｅａ／ｋ）采用由实验测定得到的反应速率与气体温度间Ａｒｒｈｅｎｉｕｓ经验关系式的可靠性问题,分析了振动热非平衡效应对于离解反应速率的影响,给出了由ＤＳＭＣ方法得到的离解反应速率与气体温度的关系曲线。     

Fe~(3+)与S~(2-)反应的研究

Fe3+ 与S2 - 反应是一个典型的竞争反应 ,反应的生成物与反应条件有着非常密切的关系。通过理论研究和实验验证 ,确认在酸性介质中反应的生成物为Fe3+ 和单质S↓ ;在碱性介质中反应的生成物为黑色Fe2 S3↓。     

对Reimer-Tiemann反应的改进

传统的Reimer-Tiemann反应产率不高(一般低于35%).通过改进反应条件,控制反应过程,使产率提高到60%,并对反应中的有关问题进行了讨论.     

基于动力学和扩散分段控制的Mg/H2O反应模型及数值分析

为了数值研究宽广温度范围内Mg/H2O的反应特性,分别建立了考虑部分MgO在液滴表面凝聚的Mg/H2O扩散燃烧模型和基于Arrhenius公式的Mg/H2O反应动力学模型.数值研究了Mg/H2O反应速率在扩散控制和化学动力学控制下随反应条件变化的规律.研究结果表明,Mg液滴扩散燃烧时间计算结果与文献值相符;提高温度和水...     

磷碳键的构建

含有磷碳键的有机磷化合物广泛应用于农药、医药、塑料添加剂等领域,构建磷碳键是有机磷化学研究的基本问题之一．概要的评述了Michaelis-Arbuzov反应、Becker反应、过渡金属催化反应和含磷氢键化合物对不饱和烯炔的加成等几种形成磷碳键的化学反应．     

制氢过程中一氧化碳氧化反应速率控制的平滑切换方法

铂族金属催化剂CO氧化过程呈现较为复杂的本质非线性属性,如反应速率突变、双稳定性和迟滞,这些本质非线性属性取决于化学反应内在的稳定性和自组织机制,所产生的一个外在结果是CO氧化反应速率与控制参数之间呈现出路径依赖的输入输出关系。对这类系统采用传统的线性控制方法具有固有的不稳定机制,可以导致化学反应速率的震荡以及控制系统的失稳;而采用常规非线性切换控制则面临在切换初始时刻所具有的大干扰问题,较大地影响控制系统的动态性能甚至稳定性。针对研究所面临的这种大干扰问题,提出基于积分初值重置的平滑切换控制方法予以解决。结果表明,所提出的方法能够从原理上解决CO氧化反应控制过程的平滑切换问题,较好地提高控制系统的动态性能。     

A quasi-isentropic model of a cylinder driven by aluminized explosives based on characteristic line analysis

A quasi-isentropic study on the process of driving a cylinder with aluminized explosives was carried out to examine the influence of the aluminum (Al) reaction rate on cylinder expansion and the physical parameters of the detonation products. Based on the proposed quasi-isentropic hypothesis and relevant isentropic theories, the characteristic lines of aluminized explosives driving a cylinder were analyzed, and a quasi-isentropic model was established. This model includes the variation of the cylinder wall velocity and the physical parameters of the detonation products with the Al reaction degree. Using previously reported experimental results, the quasi-isentropic model was verified to be applicative and accurate. This model was used to calculate the physical parameters for cylinder experiments with aluminized cyclotrimethylenetrinitramine explosives with 15.0 % and 30.0 % Al content. The results show that this quasi-isentropic model can be used not only to calculate the cylinder expansion rule or Al reaction degree, but also to calculate the physical parameters of the detonation products in the process of cylinder expansion. For explosives with 15.0 % and 30.0 % Al, 24.3 % and 18.5 % of the Al was found to have reacted at 33.9 μs and 34.0 μs, respectively. The difference in Al content results in different reaction intensity, occurrence time, and duration of two forms of reaction (diffusion and kinetic) between the Al powder and the detonation products; the post-detonation burning reaction between the Al powder and the detonation products prolongs the positive pressure action time, resulting in a continuous rise in temperature after detonation.     

基于迭代学习观测器的卫星姿态滑模容错控制

为解决卫星上反作用飞轮存在安装偏差、故障及外部干扰情况下的姿态控制问题,提出了一种基于迭代学习观测器的姿态容错控制方法。该方法通过设计迭代学习观测器,以较小的计算量实现对执行机构发生的故障以及安装偏差进行精确的估计。并利用观测器的观测结果设计滑模控制器,使处于外部干扰条件下的卫星系统在执行机构发生故障的情况下可以快速稳定地完成姿态机动任务。进一步基于Lyapunov稳定性定理证明了迭代学习观测器及控制器的全局渐近稳定性。针对反作用飞轮存在不确定性及故障的情况下进行仿真,仿真结果表明,与同类容错控制方法相比,所提方法可以更加快速精确地对故障进行估计并完成姿态控制。     

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the param-eters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0％to 15％,every 5％increase of aluminum resulted in about a 1.3％decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14％and 8％higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 μs throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12％and 2.9 μs higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80％of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.     

Shock-induced reaction behaviors of functionally graded reactive material

In this paper, the ballistic impact experiments, including impact test chamber and impact double-spaced plates, were conducted to study the reaction behaviors of a novel functionally graded reactive material (FGRM), which was composed of polytetrafluoroethylene/aluminum (PTFE/Al) and PTFE/Al/bismuth trioxide (Bi₂O₃). The experiments showed that the impact direction of the FGRM had a significant effect on the reaction. With the same impact velocity, when the first impact material was PTFE/Al/Bi₂O₃, compared with first impact material PTFE/Al, the FGRM induced higher overpressure in the test chamber and larger damaged area of double-spaced plates. The theoretical model, which considered the shock wave generation and propagation, the effect of the shock wave on reaction efficiency, and penetration behaviors, was developed to analyze the reaction behaviors of the FGRM. The model predicted first impact material of the FGRM with a higher shock impedance was conducive to the reaction of reactive materials. The conclusion of this study provides significant information about the design and application of reactive materials.