Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.     

有机羧酸钠盐对PET结晶和熔融行为的影响

采用差示扫描量热仪研究了5种具有不同取代基的苯甲酸钠盐作为结晶成核剂对聚对苯二甲酸乙二醇酯（HET）结晶和熔融行为的影响，并同滑石粉进行了对比。结果表明，成核剂的加入能明显改变PET的结晶和熔融行为。苯甲酸钠、对苯二甲酸甲酯单羧酸钠和对羟基苯甲酸钠提高既汀的熔融结晶温度（Tc）分别达22．93、21．7和19．37℃，但使PET降解严重；对苯酚钠甲酸钠能够提高Tc达17．75℃且对PET相对分子质量影响很小；对苯二甲酸二钠成核作用最差。低于滑石粉。此外，成核剂的成核能力越强，PET双熔融峰中的低温峰顶温度就越高。     

A Nonvolatile Organic Memory Device Using ITO Surfaces Modified by Ag‐Nanodots

We report on a single‐layer organic memory device made of poly(N‐vinylcarbazole) embedded between an Al electrode and ITO modified with Ag nanodots (Ag‐NDs). Devices exhibit high ON/OFF switching ratios of 10⁴. This level of performance could be achieved by modifying the ITO electrodes with some Ag‐NDs that act as trapping sites, reducing the current in the OFF state. Temperature dependence of the electrical characteristics suggest that the current of the low‐resistance state can be attributed to Schottky charge tunnelling through low‐resistance pathways of Al particles in the polymer layer and that the high‐resistance state can be controlled by charge trapping by the Al particles and Ag‐NDs.     

Performance evaluation of a water/silicone oil two‐phase partitioning bioreactor using Rhodococcus erythropolis T902.1 to remove volatile organic compounds from gaseous effluents

BACKGROUND: In the framework of biological processes used for waste gas treatment, the impact of the inoculum size on the start‐up performance needs to be better evaluated. Moreover, only a few studies have investigated the behaviour of elimination capacity and biomass viability in a two‐phase partitioning bioreactor (TPPB) used for waste gas treatment. Lastly, the impact of ethanol as a co‐substrate remains misunderstood. RESULTS: Firstly, no benefit of inoculation with a high cellular density (>1.5 g L^?1) was observed in terms of start‐up performance. Secondly, the TPPB was monitored for 38 days to characterise its behaviour under several operational conditions. The removal efficiency remained above 63% for an inlet concentration of 7 g isopropylbenzene (IPB) m^?3 and at some time points reached 92% during an intermittent loading phase (10 h day^?1), corresponding to a mean elimination capacity of 4 × 10^?3 g L^?1 min^?1 (240 g m^?3 h^?1) for a mean IPB inlet load of 6.19 × 10^?3 g L^?1 min^?1 (390 g m^?3 h^?1). Under continuous IPB loading, the performance of the TPPB declined, but the period of biomass acclimatisation to this operational condition was shorter than 5 days. The biomass grew to approximately 10 g L^?1 but the cellular viability changed greatly during the experiment, suggesting an endorespiration phenomenon in the bioreactor. It was also shown that simultaneous degradation of IPB and ethanol occurred, suggesting that ethanol improves the biodegradation process without causing oxygen depletion. CONCLUSION: A water/silicone oil TPPB with ethanol as co‐substrate allowed the removal of a high inlet load of IPB during an experiment lasting 38 days. Copyright © 2008 Society of Chemical Industry     

镁钴铝类水滑石催化合成安息香甲醚

采用共沉淀法制备了镁钴铝类水滑石化合物(MgCoAl-HTLcs),并用 X 射线衍射、扫描电子显微镜、NH_3程序升温脱附等方法对 MgCoAl-HTLcs 进行了表征,并以 MgCoAl-HTLcs 为催化剂催化苯甲醛与甲醇反应合成安息香甲醚,研究了n(Mg):n(Co):n(Al)、催化剂用量、原料配比、反应温度、反应时间对合成反应的影响。表征结果显示,MgCoAl-HTLcs 的晶相完整,表面主要为弱酸、弱碱性。催化合成安息香甲醚的适宜条件为:MgCoAl-HTLcs 催化剂用量0.10 g(约为原料总质量的0.23%),n(Mg):n(Co):n(Al)=0.4:1.6:1.0,V(苯甲醛):V(甲醇)=3:50,反应温度50℃,反应时间150 min。在此条件下,苯甲醛的平衡转化率达77.49%,安息香甲醚选择性接近100%。为洁净合成安息香甲醚开辟了一条新的途径。     

Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium （Ⅲ）

Ａｎｕｍｂｅｒｏｆｌａｎｔｈａｎｉｄｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｃｏｎ ｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｉｃａｍｉｎｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｓｉｎｃｅ1960 [1] .Ｉｎｒｅｃｅｎｔｙｅａｒｓｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｑｕａｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｌａｎｔｈａｎｉｄｅｓｂｅｃａｕｓｅｏｆｉｎ ｔｅｒｅｓｔｉｎｇｓｔｒｕｃｔｕｒｅ ,ｃｏｏｒｄｉｎａｔｉｏｎｍｏｄｅ ,ｃｏｍｐｅｔｉｔｉｏｎｒｅ ａｃｔｉｏｎａｎｄｐｒｏｐｅｒｔｙ[2～ 9] .ＥＳＲｃａｎｅ…     

Synthesis of 2,7‐Carbazolenevinylene‐Based Copolymers and Characterization of Their Photovoltaic Properties

New electroactive and photoactive conjugated copolymers consisting of alternating 2,7‐carbazole and oligothiophene moieties linked by vinylene groups have been developed. Different oligothiophene units have been introduced to study the relationship between the polymer structure and the electronic properties. The resulting copolymers are characterized by UV‐vis spectroscopy, size‐exclusion chromatography, and thermal and electrochemical analyses. Bulk heterojunction photovoltaic cells from different copolymers and a soluble fullerene derivative, [6,6]‐phenyl‐C₆₁ butyric acid methyl ester, have been fabricated, and promising preliminary results are obtained. For instance, non‐optimized devices using poly(N‐(4‐octyloxyphenyl)‐2,7‐carbazolenevinylene‐alt‐3″,4″‐dihexyl‐2,2′;5′,2″;5″,2″′;5″′,2″″‐quinquethiophenevinylene 1″,1″‐dioxide) as an absorbing and hole‐carrier semiconductor exhibit power conversion efficiency up to 0.8 % under air mass (AM) 1.5 illumination. These features make 2,7‐carbazolenevinylene‐based and related polymers attractive candidates for solar‐cell applications.     

Preparation of glucose oxidase immobilized in different carriers using radiation polymerization

Glucose oxidase (EC 1.1.3.4) was immobilized on different polymeric materials using different immobilization techniques (entrapping by γ‐irradiation, and covalent binding using epichlorohydrin). Studies were carried out to increase the thermal stability of glucose oxidase (GOD) for different applications. The activity and stability of the resulting biopolymers have been compared with those of free GOD. The effect of different polyvinyl alcohol/polyacrylamide (PVA/PAAm) compositions of the copolymer carrier on the enzymatic activity of the immobilized GOD was studied. The maximum enzymatic activity was obtained with the composition ratio of PVA/PAAm of 60:40. The behaviour of the free and immobilized enzyme was analysed as a function of pH. A broadening in the pH profile (5.5–8) was observed for immobilized preparations. The activity and stability of the resulting biopolymers produced by immobilization of GOD onto different carriers have been compared, in both aqueous and organic media, with those of the free GOD. The enzyme's tolerance toward both heat and organic solvent was enhanced by immobilization onto polymers. The addition of different concentrations of organic solvents (10–50%, v/v) to the enzyme at higher temperature (60 °C) was found to stabilize the enzyme molecule. The strongest stabilizing effect on the enzymatic activity was achieved at a concentration of 10%. Copyright © 2005 Society of Chemical Industry