纳米级TiO2粉体的制备研究——Ⅱ.絮凝剂及其浓度的影响

采用溶胶-凝胶-超临界流体干燥(SCFD)法制备纳米级TiO₂超细粉，详细考察了不同絮凝剂及其浓度对TiO₂织构和结构性质的影响。结果表明，利用强碱溶液作为絮凝剂，浓度为5 mol·L^-1是制备大孔高比表面TiO₂超细粉较为适宜的条件。     

Hybrid Xerogel Structure and Molecular Guest Dynamics

A new experimental approach to study the porosity of hybrid organic-inorganic glasses is reported. It relies upon nuclear magnetic resonance observation of molecular guest dynamics. It is shown that in MTEOS xerogels, there exists an interconnected organic-rich network in which organic guests are trapped and can eventually diffuse. The interpore translational diffusion is strongly activated and its spatial extension gives information on the pore connectivity, whose decay is characterized by the interpore jump probability given by the theoretical model.     

Coating of Tetraethylorthosilicate (TEOS)/Vinyltriethoxysilane (VTES) Hybrid Solution on Polymer Films

Tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) hybrid materials were prepared and the hydrolysis and condensation reactions during processing were investigated by means of 29Si NMR solution spectroscopy. The variation of drying characteristics of the coating films was examined with respect to the tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) ratio, as well as drying temperature, by FT-IR spectroscopy. It is shown that the TO mode of Si–O–Si stretching absorption was enhanced with increasing tetraethylorthosilicate (TEOS) content and drying temperature. Also, the wettability of the coating films on polymer films was independent of the solution composition but enhanced by the precoating of poly(4-hydroxystrene) (PHS) as a wetting agent. The adhesion between the coating and the films was also enhanced when the vinyltriethoxysilane (VTES) content in the coating solution was increased.     

Preparation of Silica-Silk Fibroin-Polyurethane Composite Films via a Sol-Gel Route

A tetraethoxysilane (TEOS)-derived sol aged for 0 h–6 h at room temperature was mixed with a polyurethane (PU) matrix. A composite of silk fibroin (SF) powders and acrylamide (AAm) was dispersed in the sol-PU mixture and dried isothermally at temperatures between 25°C and 120°C to obtain composite films. Three competitive reactions take place, i.e., those between silica-silica, SF-PU and silica-organic phases, during formation of the composite films. These reactions determine the properties such as morphology and homogeneity of the composite films. IR absorption bands for amide groups (–CONH–), C=O (amide I, 1730 cm^–1) and N–H (amide II, 1530 cm^–1) become larger with decreasing aging time of TEOS-derived sol, or increasing drying temperature. DTA exothermic peak due to the thermal decomposition of SF-AAm composite, on the composite films prepared from the 0 h-aged sol or dried at more than 50°C, shifts toward higher temperature by 44 K or more than 63 K respectively, as compared to the SF-AAm composite. Shorter aging time of TEOS-derived sol and higher drying temperature increased the extent of dispersibility, among SF-AAm composite, PU and silica, to bring a composite film more homogeneous.     

Characterization of solid standards prepared by freeze‐drying

Solid standards prepared by freeze‐drying consistently showed a high degree of homogeneity. The freezing process, completed in fractions of a second, preserves the original homogeneous distribution of the dopants, and the subsequent sublimation step would minimize any disturbance. Compared to those prepared by conventional methods such as blending and spiking, freeze‐dried standards exhibited superior lateral distribution and better uniform depth distribution. There is, however, a concentration constraint for achieving homogeneity. At 5% doping, segregation was observed in both lateral and depth distribution. Many tungsten standards doped with 10–28 elements ranging from 10 to 200 ppm were successfully prepared and used as controls for a number of analytical techniques including glow discharge mass spectrometry (GDMS) and d.c.‐arc optical emission spectroscopy (OES). Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of Copper Chromite by Vaccum Freezing Drying Method and Its Catalytic Activity for Sulfuric Acid Decomposition

Iodine sulfur (IS) process is one of the most promising routes for massive and CO₂‐free hydrogen production. Among the three reactions IS process composed, decomposition of sulfuric acid is the most energy intensive step and has to be conducted in the presence of catalyst. In this work, copper chromite (CuCr₂O₄) was prepared, characterized, and used as the catalyst for sulfuric acid decomposition reaction. The co‐precipitation preparation method of CuCr₂O₄ which featured in vacuum freezing drying (VFD), was applied, and the main factors which influence the structure of CuCr₂O₄ such as pH values of the co‐precipitation solution and calcination temperature were investigated. Results showed that pH value affected the size of copper chromite granule, when pH was between 7 and 8, the size of prepared CuCr₂O₄ was in nanometer scale. Calcination temperature influenced the purity of the crystal. The samples were characterized by XRD, TEM and BET. The catalytic activity of CuCr₂O₄ prepared by VFD was evaluated and compared with CuCr₂O₄ prepared by usual co‐precipitation method and Pt/Al₂O₃. Results showed that the activity of CuCr₂O₄ was close to that of Pt catalyst, but apparently higher than that of CuCr₂O₄ prepared by usual method. In addition, it presents good stability in the 70 h test. Therefore, it was promising to be used in the sulfuric acid decomposition step of IS process.     

高填充量碳纳米管/丁苯粉末橡胶机械混炼的物理化学机制

将用喷雾干燥法制备的碳纳米管(CNTs)/丁苯粉末橡胶复合材料在开炼机上机械混炼, 考察机械混炼对复合材料常规力学性能的影响, 并对机械混炼对CNTs增强丁苯橡胶复合材料力学性能的影响进行相应的理论研究和机理分析. 结果表明, 与混炼前的复合材料相比, 机械混炼有效地提高了CNTs/丁苯橡胶复合材料的力学性能, 特别是当CNTs加入量较大时, 提高幅度更为显著, 与填充传统补强剂CB复合材料相比, 具有较大的优势. 这是因为机械混炼一方面使CNTs在橡胶基体中获得了更为充分均匀的分散; 另一方面, 混炼过程中产生的自由基以及巨大的剪切力, 使得CNTs与橡胶基体间界面结合如物理吸附、氢键作用、化学结合等得到了进一步增强, 提高了CNTs/丁苯橡胶复合材料的结合橡胶含量, 更好地发挥了CNTs对丁苯橡胶的补强效应, 从而提高了复合材料的拉伸强度和撕裂强度等力学性能. CNTs补强丁苯橡胶复合材料力学性能的机理符合“强键和弱键学说”.     

Synthesis of transparent silica aerogels using tetraalkylammonium fluoride catalysts

Tetraalkylammonium fluoride salts have been employed as catalysts for the synthesis of silica aerogels by a two-step, sol–gel method. Aerogel materials were characterized by N₂ physisorption and SEM. The effect of the type of catalyst on the optical transparency of obtained aerogels has been examined. It has been found that such compounds allow the synthesis of silica aerogels with the highest optical transmittance ever reported for such materials. The optimal catalysts are tetrabutyl and tetraoctyl ammonium fluoride, with which aerogels with transparency as high as 96% and extinction coefficient as low as 3.5 m⁻¹ can be prepared.     

Indirect evidence of supramolecular changes within cellulose microfibrils of chemical pulp fibers upon drying

Dried and never-dried chemical pulps were subjected to strong sulfuric acid hydrolysis and the dimensions of the resulting cellulose nanocrystals (CNCs) were characterized by AFM image analysis. Although the average length of CNCs was fairly similar in all samples (55–65 nm), the length distribution histograms revealed that a higher number of longer crystals and a lower number of shorter crystals were present in the CNC suspensions prepared from never-dried pulps. The distinction was hypothetically ascribed to tensions building in individual cellulose microfibrils upon drying, resulting in irreversible supramolecular changes in the amorphous regions. The amorphous regions shaped by tensions were deemed as more susceptible to acid hydrolysis.     

Molecular associations in acacia gums

The tendency of polysaccharides to associate in aqueous solution has long been recognised. Molecular associations can profoundly affect their performance in a given application due to its influence on the molecular weight, shape and size. This will ultimately determine how the molecules will interact with each other, with other molecules and with water. There are several factors, such as hydrogen bonding, hydrophobic association, ion mediated association, electrostatic interaction, concentration dependence and the presence of proteinaceous components, which affect this behaviour. Our objective is to highlight the role of the proteinaceous component, present in acacia gum, to promote associations when the gum is subjected to various processing treatments such as maturation, spray drying and irradiation. The results demonstrate the ability of the proteinaceous component to promote hydrophobic associations which influence the size and proportion of the arabinogalactan high molecular weight component (AGP). Heat treatment in solid state (maturation) increases the hydrophobic character of the gum and hence its emulsification performance. Spray drying also involves aggregation through hydrophobic association but changes the surface properties of peptide moieties to become more hydrophilic compared to the association promoted by the maturation treatment in the solid state. Irradiation induced cross-linking, in the presence of unsaturated gas, was used to introduce C–C bonds into the carbohydrate moiety and thus confirms the hydrophobic association prompted by the heat used in the maturation and spray drying. This association can be reversed by treatments, such as filtration or high pressure homogenisation. The results reported here reconcile the contradiction about structure of gum arabic proposed by the wattle-blossom and twisted hairy rope models and shows that the AGP fraction is basically an aggregated fraction made up of AG units stabilized by low molecular weight highly proteinaceous components.