Synthesis of self‐photosensitizing polyesters containing donor–acceptor norbornadiene moieties and benzophenone groups and their photochemical reactions

The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007     

Photochemical deprotection of nitro-substituted benzenesulfenates via photoinduced electron transfer

The photochemical deprotection of alkyl 2,4-dinitrobenzenesulfenate or alkyl 2-nitrobenzenesulfenate was successfully achieved by addition of triethylamine, while it was unsuccessful without triethylamine. The sulfur-oxygen bond cleavage is thought to occur heterolytically in the sulfenate anion radical produced by photoinduced electron transfer with triethylamine.     

Growth process of TiC clusters from Ti nanoparticles with evaporated carbon layer

Titanium carbide formation by the solid–solid reaction on the surface of Ti nanoparticles was studied in situ using a high-resolution transmission electron microscope with a heating stage. The cross-sectional image of the Ti surface was clearly observed. Vacuum-deposited carbon covered the whole the surface of Ti nanoparticles in spite of the partly evaporation on the nanoparticle surface. The diffusion of the carbon atoms inside the Ti nanoparticles depended on the size of the nanoparticles. When the Ti nanoparticle diameter was less than 30 nm, carbon atoms diffused into the Ti nanoparticle and formed TiC. The superstructure of the Ti nanoparticles was observed, which revealed the growth process of TiC to be the diffusion of carbon atoms. For Ti nanoparticles with diameter larger than 30 nm it was observed that diffusion of Ti atoms into the carbon layer was dominant, which resulted in formation of TiC in the carbon layer at the surface of Ti nanoparticles.     

CO（ a）+ NO（X）传能体系中的新传能通道

在相对碰撞平动能为 0 .0 5eV的分子束实验条件下 ,研究了亚稳态CO(a) +NO(X)的E E传能通道 .通过测量和分析交碰区的传能发射光谱 ,在 780和 860nm处观测到了NO(b -a)跃迁Ogawa带的△v =+ 4和△v =+ 3序的发射光谱 .从而首次在实验上直接证实了传能过程中第四通道的存在 (CO (a) +NO(X)→CO (X) +NO(b) ) .这一通道的发现解释了前人测量到的在CO(a)与NO(X)碰撞传能过程中CO(a)的猝灭速率远大于NO(A ,B)生成速率的实验结果 ,并进一步证实了这一“经典”E E传能体系为电子交换机理的传能观点     

35Cr25Ni12奥氏体耐热钢中碳化物的电子显微分析

应用扫描电镜（SEM）和透射电镜（TEM）研究了长期使用前后的35Cr25Ni12奥氏体耐热钢中的碳化物演变行为；该钢固溶时效后的组织由初晶奥氏体及M23C6共晶碳化物组成，奥氏体基体中析出了二次M23C6，二次碳化物总是与基体保持立方－立方取向关系；长期使用（3、5年）后，奥氏体中析出的二次碳化物量明显增加，部分M23C6已转变为M6C，M6C与奥氏体基体以及二次碳化物M23C6保持[001]M6C//[221]A//[221]M23C6孪晶取向关系。     

Sn/Ge(1 1 1) α-phase: characterization of image resonances by specular electron reflection and selective electron scattering

Image potential resonances on the Sn/Ge(1 1 1) α-phase are investigated by two closely related methods: specular electron reflection and so-called selective electron scattering. Electrons from image resonances are detected on this surface at 120 and 300 K, i.e. below and above the phase transition at about 200 K. The dispersion of the image resonances reveals at these two temperatures equivalent effective electron masses, which are characteristic for this type of electronic surface states. The results of the two methods are consistent according to the similarity of the scattering processes. Changes in the loss peak intensity with the annealing temperature are assigned to the surface quality and are reflected by characteristic photoemission intensities.     

Enhancement of the emission yield of silicon nanocrystals in silica due to surface passivation

The ability of surface passivation to enhance the photoluminescence (PL) emission of Si nanocrystals in SiO₂ has been investigated. Silicon precipitation in implanted samples takes place in a time scale of few minutes at 1100°C. For longer annealing at the same temperature, the PL intensity of the Si nanocrystals increases and eventually reaches saturation, while it correlates inversely with the amount of Si dangling bonds at the Si–SiO₂ interface (P_b centers), as measured by electron spin resonance. This combined behavior is independent on the silica matrix properties, implantation profiles and annealing atmosphere and duration. The observation that the light emission enhancement is directly related to the annealing of P_b centers is confirmed by treatment in forming gas. This mild hydrogenation at much lower temperature (450°C) leads to a complete passivation of the P_b defects, increasing at the same time the PL yield and the lifetime.     

Au等离子体M带5f-3d跃迁的电子离子碰撞激发速率系数

电子离子碰撞激发速率系数在超组态碰撞辐射模型中真实模拟非局域热动力学平衡Au激光等离子体M带谱 5f 3d跃迁中各种复杂电荷态离子的电离态特性 (譬如离子的平均电离度 ,相对丰度和能级布居数 )是必不可少的。基于准相对论多组态Hartree Fock方法和扭曲波玻恩交换近似 ,采用自编的扭曲波程序ACDW (9)和Fit(9) ,从头计算了Au等离子体M带 5f 3d电子离子碰撞激发速率系数。结果表明 :在“神光II”实验装置诊断的电子温度约 2keV ,电子密度约 6× 10 2 1cm-3 范围内 ,这些电子离子碰撞激发参数有利于采用超组态碰撞辐射模型模拟Au的激光等离子体M带 5f～ 3d细致谱的平均电离度和电荷态分布。     

Solid state phase equilibria in the Gd-Si-B system at 1270 K

Solid state phase equilibria in the ternary Gd-Si-B phase diagram have been proposed at 1270 K using X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Prior to this work, the binary systems Gd-B, Gd-Si and Si-B have also been reinvestigated. The main characteristic of the ternary diagram is the occurrence of two new ternary compounds Gd₅Si₂B₈ and Gd₅Si₃B_0.64. The former crystallizes in tetragonal symmetry, space group P4/mbm with unit cell parameters a=7.2665(3), c=8.2229(7) Å, the second one presents hexagonal symmetry, space group P6₃/mcm with unit cell parameters a=8.5080(4),c=6.4141(2) Å. The X-ray structures of the two structurally related phases Gd₅Si₃B_0.64 and host binary Gd₅Si₃ have been refined from three-dimensional single-crystal intensity data to the final R values of 0.036 (R_w=0.046) and 0.046 (R_w=0.055) for 457 and 401 reflections, respectively with [F>4σ(F)]. Both structures exhibit the Mn₅Si₃-type structure, with in addition for Gd₅Si₃B_0.64 a partial occupancy by boron of the normally vacant interstitial site at the center of the Gd₆ octahedron, which corresponds to the origin of the unit cell. Bonding between the interstitial boron atoms and the gadolinium ones forming the Gd₆B polyhedra is indicated by the decrease in the corresponding Gd-Gd distances and consequently in the unit cell volume. Finally, the Gd-Si-B phase diagram is compared with the previously reported Er-Si-B, at 1070 K.     

Electron diffraction investigation of PPTA/nylon 3T blends from shear-oriented anisotropic solutions

Nematic solutions of PPTA and nylon 3T were prepared in H₂SO₄ Optical microscopy was used to ascertain the phase behaviour of the blends. In the studied concentration range, no phase separation was observed. The solutions were shear-oriented and coagulated, and the resulting samples were studied by x-ray and electron diffraction. Nylon 3T crystallised even at a low concentration, which is indicative of a phase separation. Electron diffraction investigations of the oriented samples showed that well-oriented areas, which were predominantly composed of PPTA, adjoined areas where the major component, nylon 3T, showed no orientation. The relative proportion of the unoriented areas increased with increasing nylon concentration. It was concluded that, upon coagulation, the nylon was segregated into separate phases and crystallised unoriented, whereas for PPTA, crystallisation proceeded with very little chain rearrangement therefore preserving the orientation.