Comparative behavior of polybutadiene and polynorbornene‐based latices prepared by dispersion ring‐opening metathesis polymerization with a poly(ethylene oxide) macromonomer

This study critically examines the similarities and differences between poly(ethylene oxide) (PEO) stabilized latices of polynorbornene and polybutadiene. Features such as the kinetics of copolymerization of norbornene and cyclooctadiene with a macromonomer of PEO, the particles' size and morphology, the type of copolymer formed, and the stability of these latices were investigated and the results obtained are considered. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2705–2716, 2004     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Study on the Superhydrophilicity of the SiO2-TiO2 Thin Films Prepared by Sol-Gel Method at Room Temperature

Nanoscale SiO₂-TiO₂ composite thin films with the thickness of about 100 nm were prepared by sol-gel method at room temperature in air. The chemical states of the elements on the surface and near the surface were measured by XPS. The results showed that the Ti on/near the surface of the thin films existed not only as TiO₂ but also as Ti₂O₃. Part of the TiO₂ was changed to Ti₂O₃ after UV irradiation. The crystalline structure of the TiO₂ in the SiO₂-TiO₂ thin films was anatase with the crystallite size of 14–20 nm. It was found that the thin film prepared at room temperature in air has good superhydrophilic property and has strong adherence to the substrate.     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

三维光晶格中玻色凝聚气体基态波函数及干涉演化

基于Gross-Pitaevskii方程，运用有效化学势概念，研究了囚禁在组合势(由磁阱和三维光 晶格组成)中玻色凝聚气体在三维光晶格中的分布规律，并由此得到玻色凝聚气体的归 一化基态波函数.在取消组合势和仅取消光晶格而保留磁阱的两种情况下，运用传播子方 法求解出玻色凝聚气体密度分布的解析表达式.取消组合势后，理论计算所得到的玻色凝聚 气体聚随时间的演化规律与Greiner等的实验结果相一致.仅取消光晶格而保留磁阱时，研 究表明玻色凝聚气体的干涉模式呈现周期性的振荡行为.此外，在磁阱为各向异性的情况下 ， 关键词： 玻色凝聚气体 磁阱 光晶格 干涉模式     

旋光性与电光效应交互作用及其对旋光晶体电光Q开关的影响

研究了晶体的旋光性与电光效应的交互作用、以及此交互作用对 旋光晶体电光Q开关的影响. 关键词： 旋光性 电光效应 电光Q开关 3Ga₅SiO₁₄晶体')" href="#">La₃Ga₅SiO₁₄晶体     

Syntheses, Characterization and Crystal Structures of Two-dimensional 4,4''-Bipyridyl Lead Halides,PbI2 (4,4'' -bpy) and PbBr2 (4,4'' -bpy)

Two-dimensional 4,4-bipyridyllead halides, PbI2 (4,4'-bpy) (1) and PbBr2 (4,4'-bpy) (2), were synthesized. The structures were determined by means of X-ray single crystal diffraction.The structure shows a distorted octahedral configuration with six-coordinated central lead atoms. In crystals 1 and 2, the molecules are packed in a two-dimensional network structure through bridging halide atoms and 4,4'-bipyridine ligands between the adjacent lead atoms.