显微拉曼光谱法研究盐酸丁咯地尔的热降解历程

本文采用显微激光拉曼光谱、红外光谱和热重技术等多种分析方法,对盐酸丁咯地尔的热降解机理进行了较为详细的研究。通过对原药及其热氧降解历程中间产物的拉曼光谱、红外光谱分析,证实了盐酸丁咯地尔的热氧降解过程与热重分析实验的结果基本相符。热降解过程分为两个明显的阶段:第一阶段是盐酸丁咯地尔脱盐酸、脱羧裂解,剩下苯环骨架结构;第二阶段是苯环骨架完全氧化裂解。     

β-DDB及其衍生物的结构与红外光谱特征

总结归属了肉豆寇醚酸甲酯、6－Br肉豆寇醚酸甲酯、β-DDB（6,6′－二甲氧基－4,5,4′,5′－二次甲二氧基－2,2′－二甲氧羰基联苯）及其5种衍生物的主要红外吸收谱带和特征,讨论了其红外吸收频率随化合物结构变化的规律。 结果表明分子中酯基的改变主要对羰基的伸缩振动频率有较大的影响,而对苯环的骨架振动影响较小;当苯环上H原子被其他取代基取代时,羟基及苯环的骨架吸收均发生显著变化。     

聚-α-甲基苯乙烯热降解产物研究

 降解芯轴技术是制备激光惯性约束聚变靶丸的重要技术之一。采用热分析技术研究了聚-α-甲基苯乙烯（PAMS）热降解温度,采用裂解色谱-质谱联用技术分析了PAMS的热降解产物。研究表明：PAMS降解温度范围为260～320 ℃,在此温度下PAMS降解产物主要是α-甲基苯乙烯单体,另外还有微量四氢呋喃溶剂残留及α-甲基苯乙烯二聚体。因主链上季碳原子的存在,PAMS的热降解过程以端基裂解的解聚反应为主,单体产率超过99%。     

基于热重红外联用分析的生物质热裂解机理研究

利用热重红外联用技术在线分析研究了白松在不同升温速率下的热裂解行为,结果表明木材的热裂解可归结于纤维素、半纤维素和木质素三种主要组分的热裂解。白松的热裂解产物主要有酸类、醇类、醛类、酮类、酯类、水分和小分子气体等。在线红外分析结果表明白松热裂解过程中先析出游离水,随后发生解聚和脱水反应,主要的苷键和碳碳键断开形成各种烃类、醇类、醛类和酸类等物质,随后,这些大分子物质又二次降解为一氧化碳为主的气体产物。     

生物质液相解聚残渣热解行为对比研究

解聚残渣是生物质在酸催化转化制取平台化合物过程中形成的固体副产物.本次研究发现三种衍生自玉米杆(H-CS)、柳桉(H-ES)、樟子松(H-PS)的解聚残渣都是富含苯环和呋喃环的复杂聚合物,其碳含量超过68％.基于DG-DAEM的热裂解宏观动力学特性模拟表明H-CS降解平行反应具有更低的活化能(144.7 k J/mol),而缩合平行反应是H-CS的主导反应.此外,还使用PY-GC/MS和TG-TOF-MS对热解产物的逸出行为进行了分析,得到解聚残渣中典型化学结构与热解行为之间的关联.     

乙炔高温裂解的从头算动力学模拟

本文采用了从头算动力学结合量化计算来研究乙炔的热裂解,发现了一条通过连续乙烯基卡宾加成生成苯环的机理,并和与这条路径相竞争的路径进行了对比. 此外,还得到了乙烯基卡宾的寿命.     

乙炔高温裂解的从头算动力学模拟（英文）

本文采用了从头算动力学结合量化计算来研究乙炔的热裂解,发现了一条通过连续乙烯基卡宾加成生成苯环的机理,并和与这条路径相竞争的路径进行了对比.此外,还得到了乙烯基卡宾的寿命.     

超声波和紫外光协同降解酸性橙Ⅱ水溶液的机理研究

以含有多个苯环的典型偶氮染料-酸性橙Ⅱ为研究对象,研究了超声波和紫外光分别辐照及共同辐照下的降解现象。酸性橙Ⅱ水溶液在超声波及紫外光分别辐照下均发生显著降解,反应过程符合准一级反应动力学规律。在超声波和紫外光共同辐照下,反应过程也符合准一级反应动力学规律,同时酸性橙Ⅱ水溶液降解呈现显著的声光协同效应,即同一辐照时间内超声波和紫外光共同辐照下酸性橙Ⅱ的降解率大于超声波和紫外光单独辐照下各自降解率之和。动力学分析结果表明,该协同效应可归因于紫外光对超声空化过程中产生的过氧化氢的裂解作用。      

红外光谱中取代基对苯环骨架振动吸收峰的影响规律

本文初步地探讨了单取代及对位双取代对苯环骨架振动吸收峰频率和强度的影响规律 ,得出结论 :1给电子单取代基随给电子能力增强使苯环骨架振动吸收峰 16 0 0 cm-1增强 ,而吸电子基则相反。 2卤素作为单取代基时 ,使苯环骨架伸缩振动产生强红外吸收峰 ;且随卤素电负性增强吸收峰频率向高波数移动。 3对位取代基为不同类型时 ,16 0 0 cm-1处显强峰 ,而为同一类型时 ,当电子效应相近或相同时 ,16 0 0 cm-1处吸收峰很弱或根本无吸收峰。并讨论了产生这些现象的原因。     

不同气氛下裂解含苯环聚硅氧烷制备锂离子电池Si-O-C复合负极材料的电池性能研究

在惰性气氛Ar和还原性气氛H₂中通过高温裂解含苯环的聚硅氧烷分别制备了硅氧碳化物Si-O-C复合负极材料,并且采用了元素分析element analysis、广角粉末X射线衍射XRD、傅里叶激光拉曼光谱Raman等手段表征了二者组成和结构的差别.实验发现,在H₂气氛中裂解制备的Si-O-C复合负极含有较高的可逆、较低的不可逆容量,而且可逆容量随温度的增加而增长.其中H₂气氛中1000 ℃情况下制备的Si-O-C复合负极的可逆容量622 mAh/g,首次库仑效率59%.Si-O-C复合负极的不可逆容量与氧的含量相关,可逆容量可能与碳含量及碳结构,以及SiOC中硅的结构相关.在H₂气氛中制备的Si-O-C负极材料是一种潜在的锂离子电池的负极材料. 关键词： 硅氧碳化物 负极材料 锂离子电池     

两种含硅炔基树脂的固化行为研究

综合采用红外光谱（FTIR）、核磁碳谱 (13C NMR)、差示扫描量热（DSC）,热失重测试(TGA)等多种表征手段,研究了聚硅芳炔（PAR）和聚硅乙炔（PMR）两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明：PAR和PMR树脂的固化机理不同,PAR主要通过炔基间的加成和Diels-Alder反应实现分子间的固化交联,并最终形成由苯环和稠芳环组成的芳构网络;PMR则主要通过硅氢基、炔基、烯基之间的加成反应实现固化,并成形饱和的碳硅Si—C(sp3)网络结构。固化成型的芳构网络和Si—C(sp3)网络结构分别赋予了PAR和PMR树脂固化物良好的热稳定性能,它们的热分解温度T_d5均大于600 ℃,900 ℃残重率均达到85%以上。     

热解吸气相色谱法测定皮鞋厂室内的苯含量

采用热解吸气相色谱法分别测定皮鞋厂成型车间、缝制车间和配料车间空气中的苯含量.用活性炭吸附管采集样品,并放入热解吸仪中加热,通氮气解吸出苯,用气相色谱仪FID检测器分析.结果表明,采样量为10L时,热解吸气相色谱法的平均解吸效率为97.5％,精密度和灵敏度均较高,适用于工作场所中苯浓度的测定.检测数据显示3个场所的苯浓度均符合国家标准.     

The structure of benzene on Rh(111): Coadsorption with CO

The molecular structure of benzene coadsorbed with CO on Rh(111) has been investigated by angle resolved UV photoemission (ARUPS), LEED and thermal desorption spectroscopy. The symmetry of the benzene adsorption complex in a mixed benzene-CO (3×3) LEED structure has been determined to C_6v by ARUPS. This indicates that the benzene molecules remain essentially undistorted in the CO coadsorbate layer, as it has been found for the pure benzene layer on Rh(111).     

Carbon monoxide induced ordering of benzene on Pt(111) and Rh(111) crystal surfaces

Carbon monoxide induced ordering of an organic molecule, benzene, has been studied on the Pt(111) and Rh(111) crystal surfaces using low-energy electron diffraction, high-resolution electron energy loss spectroscopy, and thermal desorption spectroscopy. We propose detailed geometries for all the ordered structures of coadsorbed CO and benzene. Ordering in the adsorbed overlayer is proposed to result from the interactions between adsorbed CO molecules in the presence of benzene.     

Benzene and thiophene formation from acetylene on sulfided Pd(111) studied by LITD/FTMS

We report the first laser-induced thermal desorption (LITD) studies of acetylene on Pd(111). LITD coupled with Fourier transform mass spectrometry (FTMS) probes the surface molecular composition. Our results show simultaneous formation of thiophene and benzene at 120 K after a 6 L dose of acetylene at 80 K on a Pd(111) surface with 0.06 ML of sulfur. Simultaneous formation implies that formation of the C₄H₄ intermediate is the slow step in the formation of both cyclic products. The relative amounts of thiophene and benzene observed with LITD/FTMS are comparable, while thermal desorption spectroscopy (TDS) yields integrated thiophene signals that are < 2% as intense as for benzene. This indicates that thiophene primarily decomposes upon heating. Low coverage (0.5 L) results confirm reports that the presence of sulfur enhances benzene production.     

Imaging benzene on nickel and copper {110} surfaces with low temperature STM:: the adsorption site

Single benzene molecules have been imaged on the {110} surfaces of both copper and nickel with an Eigler-type low temperature scanning tunnelling microscope. Conditions were chosen such that the molecule and the lattice atoms could be resolved at the same time within one image frame. On Ni{110} benzene was found to adsorb in the hollow site between the close-packed rows. For the more weakly bound molecule on Cu{110} the imaging conditions had to be changed since, for the tunnelling conditions under which the lattice atoms are resolved, a strong interaction between the tip and the benzene takes place. This results in the molecule being “dragged” along the surface. By changing the tunnelling conditions within one image frame, however, it is possible via extrapolation of the substrate lattice to show that the molecule adsorbs in the long-bridge site. The shapes of the images of individual molecules are discussed.     

Experimental study of inspection on SiC coated high-temperature alloy plates with defects using pulsed thermographic technique

The pulsed thermographic technique was used to detect flat-bottomed hole defects in SiC coated high-temperature alloy plates. Temperature–time Logarithm Fitting Method (TtLFM), Principal Component Analysis (PCA) and Pulsed Phase Thermography (PPT) were used to extract the characteristic information of the thermal wave signal generated by thermal pulse. It is found that PCA algorithm is available for analyzing the thermal wave signal generated by thermal pulse due to higher signal–noise ratio. Experiments were performed to investigate the effect on the thermal contrast by the pulse intensity, frame rate and analysis moment, respectively. Experimental results show that larger pulse intensity and frame rate are benefit to get larger thermal contrast thermogram, and optimal analysis moment selected is helpful to detect the defects of SiC coated high-temperature alloy plates using pulsed thermographic technique.     

基于无基底焦平面阵列红外热像仪的理论模型分析

基于双材料微悬臂梁热变形原理的光学读出非制冷红外探测阵列经历了从有基底结构向无基底结构的发展过渡,无基底阵列的红外成像结果和有限元模型分析均表明无基底阵列不满足恒温基底条件.本文结合电学比拟的方法,提出了一种新的基于无基底焦平面阵列(focal plane Array,FPA)的热传递分析的理论模型.分析采用整体考虑的思路,避开了无基底FPA阵列各单元热传递互相影响所产生的复杂热分布分析,并考虑了框架对热量的吸收与传递.理论模型采用外边框与环境等温的边界条件,虽不及有限元方法对边界条件的处理灵活,但也已取 关键词： 光学读出 无基底 非制冷红外成像 焦平面阵列     

Revised intermolecular potential with parameters depending on partial atomic charges for aromatic molecular systems

The practicablity and precision of the intermolecular potential was improved within the frame of an atom-atom approximation using 6-exp-1 type isotropic interatomic potentials without additional parameters. The improvement involves making the van der Waals parameters functions of the partial charges on constituent atoms supplement the classification of the parameter set, depending on atom type. The validity of the potential was confirmed with respect to crystal structures of polyacene (i.e., benzene, naphthalene, anthracene and tetracene) by molecular dynamics simulations.