Morphology and activity of nanosized NdCl3 catalyst for 1,3‐butadiene polymerization

The binary lanthanide catalyst for 1,3‐butadiene was invented for 40 years ago. However, it has not been employed in commercial application due to its poor solubility and low activity. Nanosized neodymium chloride (NdCl₃) was prepared in tetrahydrofuran (THF) medium through dissolution, chelation, and colloidal formation steps. Anhydrous NdCl₃ was dissolved in THF, and ca. 1.5 THF molecules were coordinated. In the colloidal formation step, THF was slowly replaced with the addition of cyclohexane, and pale blue nuclei, nanosize below 200 nm, were formed. The structural studies for NdCl₃ · xTHF using X‐ray powder diffraction (XRD) and scanning electron microscope (SEM) indicate that high ordered crystallinity is decreased with reduced particle size from trigonal prismatic to porous sphere structure. Nano NdCl₃, obtained as colloidal state in cyclohexane, was activated with Al(iBu)₃ and Al(iBu)₂H at room temperature and employed for 1,3‐butadiene solution polymerization. The nanosized Nd catalysts showed high activity (1.0 ～ 1.3 × 10⁵ g/Nd mol · h), which is comparable to that of the ternary neodymium catalyst Nd(neodecanoate)₃/AlEt₂Cl/Al(iBu)₃. The microstructures of polybutadiene, cis, trans, and vinyl, are about 96.0, 3.5, and 0.5%, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1279–1283, 2005     

The flexible surface or the rigid surface?

In this paper we discuss aspects of the concept described by Somorjai as the flexible surface, and whether some surfaces can be considered to be inflexible, or rigid. We present STM results which appear to manifest both types of behaviour for surfaces, depending on their oxidation state. Copper metal surfaces can be classed as flexible, showing facile reconstruction in the presence of oxygen, whereas an oxidised Pd(110) surface shows no apparent diffusivity, even at 500 K. We go on to show data for a bulk oxide which indicates that sub-stoichiometry in the sample induces an element of flexibility in the surface, especially during reaction with oxygen. Finally, this is related to the direct observation of spillover on model catalysts of Pd nanoparticles supported on TiO₂. It must be recognised that flexibility relates to surface diffusivity and hence length- and time-scales. Surfaces which appear inflexible at short times may be flexible at long times. In relation to catalysis then, surface flexibility depends on the relationship between the time-scale of diffusive events on the surface and the catalytic turnover number.     

基于表面等离子体共振传感器的尿微量白蛋白检测

检测尿微量白蛋白(MAU)可对轻微肾脏损害进行早期诊断,也可对高血压患者可能发生的心脑血管事件进行预测。实验将抗体通过巯基自组装固定于Au膜表面,研制了一种快速检测MAU的表面等离子体共振(SPR)生物传感器。结果表明:直接检测法可以检测到0.3μg/L的MAU,而纳米Au放大法检测限可以低至0.03μg/L。     

Preparation and characterization of TiO2 and polymer nanocomposite films with high refractive index

Novel nanocomposite films of TiO₂ nanoparticles and hydrophobic polymers having polar groups, poly (bisphenol‐A and epichlorohydrin) or copolymer of styrene and maleic anhydride, with high refractive indices, high transparency, no color, solvent‐resistance, good thermal stability, and mechanical properties were prepared by incorporating surface‐modified TiO₂ nanoparticles into polymer matrices. In the process of preparing colloidal solution of TiO₂ nanoparticles, severe aggregation of particles can be reduced by surface modification using carboxylic acids and long‐chain alkyl amines. These TiO₂ nanoparticles dispersed in solvents were found not to aggregate after mixing with polymer solutions. Transparent colorless free‐standing films were obtained by drying a mixture of TiO₂ nanoparticles colloidal solution and polymer solutions in vacuum. Transmission electronic microscopic studies of the films suggest that the TiO₂ nanoparticles of 3–6 nm in diameter were dispersed in polymer matrices while maintaining their original size. Thermogravimetric analysis results indicate that the nanocomposite film has good thermal stability and the weight fraction of observed TiO₂ nanoparticles in the film is in good accordance with that of theoretical calculations. The refractive index of nanocomposite films of TiO₂ and poly(bisphenol‐A and epichlorohydrin) was in the range of 1.58–1.81 at 589 nm, which linearly increased with the content of TiO₂ nanoparticles from 0 to 80 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Phase characterization and mechanical and flame‐retarding properties of nano‐CaSO4/polypropylene and nano‐Ca3(PO4)2/polypropylene composites

An in situ deposition approach was used for the synthesis of nano‐CaSO₄ and nano‐Ca₃(PO₄)₂. The nanosize particles were confirmed with an X‐ray diffraction technique. Composites of polypropylene (PP) with 0.1–0.5 wt % nano‐ or commercial CaSO₄ or nano‐Ca₃(PO₄)₂ were prepared. The transition from the α phase to the β phase was observed for 0.1–0.3 wt % nano‐CaSO₄/PP and nano‐Ca₃(PO₄)₂/PP composites. This was confirmed by Fourier transform infrared. A differential scanning calorimetry analysis was carried out to determine the thermal behavior of the nanocomposites with increasing amounts of the nano‐CaSO₄ and nano‐Ca₃(PO₄)₂ fillers. Increases in the tensile strength and Young's modulus were observed up to certain loading and were followed by a decrease in the tensile strength. A continuous decrease in the elongation at break (%) was also observed for commercial CaSO₄ and larger nano‐Ca₃(PO₄)₂. A decrease in the mechanical properties after a certain loading might have been due to the agglomeration and phase transition of PP in the composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 670–680, 2007     

Photoluminiscent Manganese Nanoparticles from Solid State Polyphosphazenes Organometallic Derivatives

Pyrolysis in air at 800°C of [{NP(OC₁₂H₁₀)}_0.6{NP(OC₆H₄PPh₂·(π-CH₃C₅H₄)−Mn(CO)₂)₂}_0.4] _n (1) in the solid state affords product 2 containing nanoclusters of Mn₂P₂O₇ with sizes ranging from 50 to 90 nm and averaging about 74 nm. The egg-shape of the unpyrolyzed organometallic polymer is retained but with increased particle size after pyrolysis. The pyrolytic material shows near-infrared photoluminescence attributed to the emission of tetrahedral Mn²⁺ embedded in a matrix of Mn₂P₂O₇. The solid-state pyrolysis of organometallic derivatives of polyphosphazenes may be a useful and general route to nano-structured Mn₂P₂O₇. An erratum to this article can be found at     

纳米粒子增韧聚氯乙烯研究新进展

本文主要综述了纳米粒子在聚氯乙烯增韧改性中的应用研究状况.现有的结果表明,纳米复合技术在聚氯乙烯增韧改性中具有同时提高材料韧性和强度的特点.因此,纳米复合技术将成为聚氯乙烯增韧改性的一种重要方法,并得到广泛应用.     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synergic influence of a surfactant and ultrasonication on the preparation of soluble,conducting polydiphenylamine/silica‐nanoparticle composites

Conducting polydiphenylamine was used to encapsulate silica nanoparticles through the oxidative polymerization of diphenylamine in the presence of ultrasonic irradiation. The polymerization was performed in the presence of sodium lauryl sulfate as a surfactant. Experiments performed in the absence of ultrasound clearly demonstrated that the application of ultrasonication played multiple roles in the preparation of a composite of polydiphenylamine with silica nanoparticles. Ultrasonication dispersed the silica nanoparticles, converted sodium lauryl sulfate to lauryl alcohol, and augmented the dispersion of the silica‐nanoparticle/polydiphenylamine composite in an organic medium. Silica‐nanoparticle/polydiphenylamine composites were also prepared in the absence of ultrasound and/or sodium lauryl sulfate. The silica‐nanoparticle/polydiphenylamine composites were characterized with Fourier trans form infrared spectroscopy, ultraviolet–visible/near‐infrared spectroscopy, and thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3912–3918, 2006     

热处理条件对硅酸盐玻璃中原位形成银纳米颗粒的影响

用离子交换结合热处理法制备银(Ag)纳米颗粒-玻璃复合材料.用透射电镜、高分辨透射电子显微镜、Ruthefford背散射谱和紫外-可见光吸收光谱研究了热处理条件对玻璃中原位形成Ag纳米颗粒的影响.结果显示:随着热处理温度升高,玻璃表面的Ag原子逐渐向玻璃内部扩散,其表面摩尔浓度逐渐降低.提高热处理温度和延长热处理时间都有利于提高玻璃中Ag纳米颗粒的体积分数.空气中,高温热处理高掺Ag量的白玻璃样品时发生二次成核,因此,Ag纳米颗粒尺寸呈双峰分布.Ag纳米颗粒尺寸的双峰分布导致其等离子体共振吸收峰出现双峰.在氢气气氛中,在250℃热处理2min,即可在玻璃中形成大量Ag纳米颗粒,颗粒尺寸小于空气中高温热处理样品的尺寸,从而引起表面等离子体共振吸收峰发生蓝移.