基于基元反应模型的H2-O2-N2爆轰数值模拟

 采用12组分、23个化学反应的基元化学反应模型,用5阶加权本质无震荡格式（WENO）、3阶TVD Runge-Kutta格式,对H₂-O₂-N₂混合气体胞格爆轰进行了数值模拟。研究了一维ZND爆轰、自维持爆轰的详细结构以及三波点附近的流动结构。计算结果表明：由横波的压力可以显著促进二维爆轰波波阵面的形成;横波的运动生成三波点,三波点造成了爆轰的自维持传播。     

主喷管叶片中热壁面对分流管道流场特性的影响

 连续波化学激光器运转时,位于主喷管叶片内的副气流的分流管道壁面将被主喷管叶片加热而形成热壁面。通过3维的数值模拟,分析了单端、双端不同供气方式下,热壁面对分流管道流场特性的影响。热壁面将使总管气流总温沿着气流的流动方向逐渐升高,由此引起的支管入口总温的升高会降低支管的流量。无论是单端供气,还是双端供气,热壁面引起的管道流量波动幅度都要远大于绝热壁面的情况,最大波动幅度达2.16%。对进入总管的气流预热,适当增加供气总温,或将冷却管道与供气管道分开设计,气流总温变化引起的流量波动将会得到一定地抑制。     

环保型制冷剂R600a制冷系统设计及其维修工艺

大气臭氧层的破坏和温室效应的加剧,是当前世界面临的主要环境问题。文中通过对R600a制冷剂物理化学特性的介绍以及与R12制冷剂的对比,得出在冰箱领域,R600a是一种可以永久替代CFCs的环保型制冷剂,分析了R600a替代R12的制冷系统设计的一些要点,最后基于提高工作效率以及保障操作安全的考虑,阐述了R600a冰箱的维修工艺。     

Substituent effect investigation of 3‐(2, 4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one. Part 1. Correlation analysis of 13C NMR chemical shifts

A series of substituted chlorinated chalcones namely, 3‐(2,4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one, have been synthesized, X being H, NH₂, OMe, Me, F, Cl, CO₂Et, CN, and NO₂. Dual substituent parameter (DSP) models of ¹³C NMR chemical shift (CS) have revealed that π‐polarization concept could be utilized to explain the reverse field effect at CO, the enhanced substituent field effect at CO, C‐2, and C‐5, and the decreased sensitivity of substituent field effect at C‐6. Chlorine atoms dipole direction at the benzylidene ring either enhances or reduces substituent effect depending on how they couple with the substituent dipole at the probe site. The correlation of ¹³C NMR CS of C‐2, C‐5, and C‐6 with σ and σ indicates that chlorine atoms in the benzylidine ring deplete the ring from charges. Both MSP of Hammett and DSP of Taft ¹³C NMR CS models give similar trends of substituent effects at C‐2, C‐5, and C‐6. However, the former fail to give a significant correlation for CO and C‐6 ¹³C NMR CS. MSP of σ_q and DSP of Taft and Reynolds models significantly correlated ¹³C NMR CS of C_β. MSP of σ_q fails to correlate C‐1′ ¹³C NMR CS. Investigation of ¹³C NMR CS of non‐chlorinated chalcones series: 3‐phenyl‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one has revealed similar trends of substituent effects as in the chlorinated chalcones series for C‐1′, CO, C_α, and C_β. In contrast, the substituent effect of the non‐chlorinated chalcone series at C‐2, C‐5, and C‐6 did not correlate with any substituent constant. Copyright © 2010 John Wiley & Sons, Ltd.     

Conformational analysis of 4,4‐dimethyl‐4‐silathiane and its S‐oxides

4,4‐Dimethyl‐4‐silathiane and its S‐oxides [n = 0 ( 1 ), 1 ( 2 ), 2 ( 3 )] were studied experimentally by variable temperature dynamic NMR spectroscopy down to 103 K and the frozen ring inversion was revealed for all three compounds. The barriers for the degenerate ring inversion in 1 and 3 were measured to be 4.8 and 5.0 kcal/mol at the coalescence temperatures of 111 and 116 K, respectively, and practically coincide with the calculated barriers of 4.60 kcal/mol in 1 and 4.46 kcal/mol in 3 . The frozen equilibrium mixture 2‐ax/2‐eq contains 37% of the 2‐ax and 63% of the 2‐eq conformer. The ring inversion barrier proved to be ca. 4.8 kcal/mol. Calculations at the B3LYP/6‐311+G(d,p) level of theory showed the 2‐ax conformer to be 0.90 kcal/mol more stable than the 2‐eq conformer in the gas phase whereas in solution the relative stability of the conformers calculated using the PCM model at the same level of theory is inverted to become 0.19 (in CHCl₃) or 0.36 kcal/mol (in DMSO) in favor of the 2‐eq conformer. The chair–chair interconversion mechanism of sulfoxide 2 includes two intermediate energetically equivalent 1,4‐twist forms and the 2,5‐boat transition state: 2‐ax (chair) ? 2 (1,4‐twist) ? [ 2 (2,5‐boat)]^≠ ? 2 (1,4‐twist) ? 2‐eq (chair). The calculated ring inversion barriers are 5.1 ( 2‐ax → 2‐eq ) and 4.2 kcal/mol ( 2‐eq → 2‐ax ) in the gas phase, and 4.03 and 4.22 kcal/mol, respectively, in chloroform. Copyright © 2011 John Wiley & Sons, Ltd.     

不同气体环境下532nm激光诱导硅表面形貌的研究

研究了在不同气体环境下,利用532nmNd：YAG纳秒脉冲激光累积辐照单晶硅表面形成的微结构,结果表明,在其他条件相同,背景气体不同的情况下,背景气体对硅表面形貌的形成起着重要的作用。具体分析了真空、N2和SF6 3种环境气氛下形成的微结构,结果显示,在sF6中形成的锥形微结构的数密度比在N2和真空中的大,并且锥形具有更大的纵横比;在N2、真空和sF6中形成的微结构尺寸依次减小。sF6气氛下,激光辅助化学刻蚀的效率比在真空和N2气氛中的高。另外,辐照区域边缘有波纹微结构形成,分析认为,该微结构的形成是由表面张力波的冷却导致的。     

O2流量对磁控溅射N掺杂TiO2薄膜成分及晶体结构的影响

利用直流脉冲磁控溅射方法在室温下通过改变O₂流量制备具有不同晶体结构的N掺杂TiO₂薄膜,利用台阶仪、X射线光电子能谱仪、X射线衍射仪、紫外-可见分光光度计等设备对薄膜沉积速率、化学成分、晶体结构、禁带宽度等进行分析.结果表明:所制备的薄膜元素配比约为TiO_1.68±0.06N_0.11±0.01,N为替位掺杂,所有样品退火前后均未形成Ti—N相结构,N掺杂TiO₂薄膜的沉积速率、晶体结构等主要依赖于O₂流量.在O₂流量为2 sccm时,N掺杂TiO₂薄膜沉积速率相对较高,薄膜为非晶态结构,但薄膜内含有锐钛矿(anatase)和金红石(rutile)相晶核,退火后薄膜呈anatase和rutile相混合结构,禁带宽度仅为2.86 eV.随着O₂流量的增加,薄膜沉积速率单调下降,退火后样品禁带宽度逐渐增加.当O₂流量为12 sccm时,薄膜为anatase相择优生长,退火后呈anatase相结构,禁带宽度为3.2 eV.综合本实验的分析结果,要在室温条件下制备晶态N掺杂TiO₂薄膜,需在高O₂流量(＞10 sccn)条件下制备. 关键词： 2薄膜')" href="#">N掺杂TiO₂薄膜 磁控溅射 化学配比 晶体结构     

Preparation and photocatalytic property of CeO2 lamellar

A novel room temperature solid-state chemical synthesis was introduced to successfully fabricate CeO₂ samples, coupled by a polyethylene glycol 400 (PEG 400)/cetyl trimethylammonium bromide (CTAB)/sodium dodecyl sulfate (SDS). The as-prepared products were characterized by XRD, TEM, SEM, BET and UV. A study of photocatalytic degradation of the methylene blue MB under UV illumination has been carried out. It is indicated that the samples exhibit excellent photocatalytic activity. Besides, the samples assisted with surfactants possess higher photocatalytic activity than the sample without any surfactants, wherein the sample with SDS as an additive shows the highest photocatalytic activity, which is able to reach 89.6% MB degradation ratio within 60 min illumination. Moreover, the effects of important operational parameters such as initial MB concentration, catalyst loading and pH were also investigated. The above sample under the optimum conditions obtained the maximum MB degradation ratio up to 96.5%, which is higher than that of the commercial TiO₂ P25 under the same conditions. It can be concluded that CeO₂ will be a potential photocatalyst in the application of organic pollutant.     

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L_3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2p-derived states through O 2p-Cr 3d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr₂O₃ phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr₂O₃, whereas the bulk comprise phase segregations of Cr₂O₃ and/or ZnCr₂O₄, which results them the most stable TM-doped ZnO material against etching.     

Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.