新型复合分子筛的合成和催化应用

 系统地归纳总结了最近几年引起人们广泛关注的复合分子筛的研究进展,包括微孔-微孔复合分子筛、微孔-介孔复合分子筛、微孔-大孔复合分子筛及微孔-介孔-大孔复合分子筛的合成和应用近况. 并对复合分子筛的发展前景进行了展望.     

Nanoscale indentation of polymer and composite polymer-silica core-shell submicrometer particles by atomic force microscopy

Atomic force microscopy was employed to probe the mechanical properties of surface-charged polymethylmethacrylate (PMMA)-based terpolymer and composite terpolymer core-silica shell particles in air and water media. The composite particles were achieved with two different approaches: using a silane coupling agent (composite A) or attractive electrostatic interactions (composite B) between the core and the shell. Young's moduli (E) of 4.3+/-0.7, 11.1+/-1.7, and 8.4+/-1.7 GPa were measured in air for the PMMA-based terpolymer, composite A, and composite B, respectively. In water, E decreases to 1.6+/-0.2 GPa for the terpolymer; it shows a slight decrease to 8.0+/-1.2 GPa for composite A, while it decreases to 2.9+/-0.6 GPa for composite B. This trend is explained by considering a 50% swelling of the polymer in water confirmed by dynamic light scattering. Close agreement is found between the absolute values of elastic moduli determined by nanoindentation and known values for the corresponding bulk materials. The thickness of the silica coating affects the mechanical properties of composite A. In the case of composite B, because the silica shell consists of separate particles free to move in the longitudinal direction that do not individually deform when the entire composite deforms, the elastic properties of the composites are determined exclusively by the properties of the polymer core. These results provide a basis for tailoring the mechanical properties of polymer and composite particles in air and in solution, essential in the design of next-generation abrasive schemes for several technological applications.     

PVA-膨润土-KOH-H2O复合碱性聚合物电解质的制备与表征

以聚乙烯醇(PVA)与膨润土(bentonite)和氢氧化钾为原料, 采用溶液浇铸法制备了PVA-膨润土-KOH-H2O复合碱性聚合物电解质膜. 运用X衍射(XRD)、扫描电镜(SEM)和循环伏安(CV)等技术对复合膜进行了表征, 分析了膨润土对聚合物膜电导率的影响. 结果表明, 膨润土对电解质的导电性能具有双重作用: 一方面膨润土本身会阻塞PVA内部结构中的部分离子通道, 导致复合电解质的电导率降低; 另一方面, 膨润土有助于体系中KOH含量的增加, 同时PVA-膨润土相界面高导电性缺陷层的形成有助于体系电导率的提高. 当体系水的质量分数较低时, 复合电解质体系电导率存在极大值; 当w(H2O)为65%时, 则观察到电导率的线性增加趋势; 电解质最高室温电导率达0.110 S·cm-1. XRD图谱显示适当配比的复合膜中PVA呈无定形态; SEM结果证实了适当配比的复合膜中存在大量微米级孔径的微孔通道. 循环伏安曲线表明PVA-膨润土-KOH-H2O碱性聚合物电解质膜有约2.0 V的较宽电化学稳定窗口.     

Cellulose–halloysite nanotube composite hydrogels for curcumin delivery

Halloysite nanotubes (HNTs) were added to cellulose NaOH/urea solution to prepare composite hydrogels using epichlorhydrine crosslinking at an elevated temperature. The shear viscosity, mechanical properties, microstructure, swelling properties, cytocompatibility, and drug delivery behavior of the cellulose/HNT composite hydrogels were investigated. The viscosity of the composite solution increases with the addition of HNT. The compressive mechanical properties of composite hydrogels are significantly improved compared with pure cellulose hydrogel. The compressive strength of the composite hydrogels with 66.7% HNTs is 128 kPa, while that of pure cellulose hydrogel is only 29.8 kPa in compressive strength. Rheological measurement suggests the resistance to deformation is improved for composite hydrogels. X-ray diffraction and Fourier transform infrared spectroscopy show that the crystal structure and chemical structure of HNT are not changed in the composite hydrogels. Hydrogen bonding interactions between HNT and cellulose exist in the composites. A porous structure of the composite hydrogels with pore size of 200–400 μm was found by scanning electron microscopy. The addition of HNT leads to decreased swelling ratios in NaCl solution and pure water for the composite hydrogels. Cytotoxicity assays show that the cellulose/HNT composite hydrogels have a good biocompatibility with MC3T3-E1 cells and MCF-7 cells. Curcumin is further loaded into the composite hydrogel via physical adsorption. The curcumin-loaded composite hydrogels show a strong inhibition effect on the cancer cells. All the results illustrate that the cellulose/HNT composite hydrogels have promising applications such as anticancer drug delivery systems and anti-inflammatory wound dressings.     

Physicochemical and Rheological Properties of Novel Magnesium Salt-Polyacrylamide Composite Polymers

Two series of novel inorganic-organic composite polymers have been prepared through physical blending of magnesium chloride and magnesium hydroxide respectively with polyacrylamide aqueous solution. The physicochemical properties of the magnesium salt-polyacrylamide composite polymers were tuned by varying the ratio between the magnesium salt (e.g., magnesium chloride and magnesium hydroxide) and polyacrylamide. Characterizations of magnesium salt-polyacrylamide composite polymers were carried out via FTIR and TEM. Parameters such as solution conductivity and viscosity were also taken into account to characterize the physicochemical properties of the composite polymer aqueous solutions. Magnesium chloride-polyacrylamide (MCPAM) composite polymer aqueous solutions have a higher conductivity compared to magnesium hydroxide-polyacrylamide (MHPAM) composite polymer aqueous solutions. The viscosities of the MHPAM composite polymer aqueous solutions were found higher than MCPAM composite polymer aqueous solutions. The rheological properties of the composite polymer aqueous solutions were investigated using steady-state flow and oscillatory frequency sweep within the linear viscoelastic region. Shear-thinning effect was observed for both composite polymer systems when the shear rate increases. In oscillatory frequency sweep tests, both composite polymer systems show that the viscoelastic behaviors depend strongly on the magnesium salt concentrations. Viscous behavior was found to be dominant for both composite polymer systems.     

Electrochemical Properties of Hollow‐Structured MnS–Carbon Nanocomposite Powders Prepared by a One‐Pot Spray Pyrolysis Process

Spherical, hollow MnS? C composite powders were prepared from a solution of manganese salt, thiourea, and sucrose by one‐pot spray pyrolysis. The MnS? C composite powders were generated by direct sulfidation of MnO with hydrogen sulfide gas generated in situ by decomposition of thiourea during spray pyrolysis. Sucrose, which is used as a carbon source material, plays a key role in the formation of the MnS? C composite powders by improving the reducing atmosphere around the powders. Dot‐mapping images of the composite powders demonstrated uniform distribution of the manganese, sulfur, and carbon components within the MnS? C composite powder. Fine crystals of MnS were uniformly mixed with carbon derived from polymerization and carbonization of sucrose. The carbon content of the MnS? C composite powders was 26 wt %. The discharge capacities of the MnS? C composite powders in the 2nd and 200th cycles were 863 and 967 mA h g^?1, respectively, at a current density of 1000 mA g^?1. The spherical and hollow morphology of the MnS? C composite powders was completely retained, even after 200 cycles. The enhanced cycling and rate performance of the MnS? C composite powders is ascribed to the structural stability of the composite powders.     

纳米TiO2-SiO2复合氧化物的制备与性质

采用溶胶-凝胶结合CO2超临界干燥方法制备了比表面积大、热稳定性好的纳米TiO2-SiO2复合氧化物.考察了原料组成和焙烧温度对复合氧化物比表面积、热稳定性和酸性的影响,通过加氢脱硫反应考察了该复合氧化物作为加氢精制催化剂载体的可行性.结果表明,采用该方法制备的复合氧化物为纳米颗粒,在n(Ti)/n(Si)=1时,其比表面积和孔容最大;与纯TiO2相比,引入SiO2明显提高了复合氧化物的热稳定性和晶型稳定性;以此复合氧化物为载体的加氢精制催化剂具有很好的低温脱硫活性,TiO2-SiO2复合氧化物载体的酸性特征影响了催化剂的加氢脱硫活性.     

An innovative approach to utilize waste silica fume from zirconia industry to prepare high performance natural rubber composites for multi-functional applications

Silica fume (SF) is silica-rich amorphous waste by-product obtained during zirconium silicate electrofusion process. The key objective of the study was to determine the efficiency of SF as a reinforcing filler in Natural Rubber (NR) compounds vis a vis the conventional filler, high abrasion furnace (HAF) black. Inter-particle distance and particle size distribution analysis from Transmission Electron Microscopy exhibited homogeneous dispersion of filler in hybrid composite (NR SF20/HAF30) with Bis[3-(triethoxysilyl)propyl] tetrasulfide (TESPT). NR composite with 20 phr SF loading improved modulus by 107%, tensile strength by 12%, and tear strength by 28% over gum NR. Hybrid composite showed 111% increase in modulus than NR SF20 composite. Theoretical modelling of Young's modulus with volume fraction of filler quite fit with Guth-Gold equation. Hybrid composite with TESPT showed 72% reduction in heat build-up compared to NR HAF50 composite. Thermal stability improved by 6 °C and rolling resistance reduced by 64% for hybrid TESPT composite compared to NR HAF50 composite. Constrained region in NR composites obtained from dynamic mechanical analysis showed improved rubber-filler interaction in hybrid TESPT composite. Hence, this work not only provides a new approach to utilize industrial waste but also provides for a high performance NR composite at low cost.     

Electrically induced and thermally erased properties of side-chain liquid crystalline polymer/liquid crystal/chiral dopant composites

The properties of synthesized side-chain liquid crystalline polymer (SCLCP)/liquid crystal (LC)/chiral dopant composites having a chiral nematic (N*) phase at room temperature were investigated by polarized optical microscopy (POM) and a UV/VIS/NIR spectrophotometer. The composite exhibited a planar texture after it was filled into cells under homogeneous boundary conditions and it was transparent. When an electric field was applied to the composite, a focal conic texture was formed and the composite became light scattering. After the electric field was turned off, the light-scattering state remained stable for some time, i.e. the light-scattering state exhibited a memory effect. The focal conic texture changed into the planar texture when the composite was heated and the composite became transparent again. Therefore, the composite had electrically induced and thermally erased properties. The SCLCP had some influence on the memory effect and on the thermo-electro-optical properties of the composite.     

Adsorption of styrene on micron-sized, monodisperse, cross-linked polymer particles in a snowman-shaped state by utilizing the dynamic swelling method

Polystyrene/styrene–divinylbenzene copolymer composite particles with different cross-linking densities were produced by seeded copolymerization for (styrene/divinylbenzene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method (DSM) which was proposed by the authors in 1991. Using the cross-linked, composite particles as seeds, styrene-adsorbed (swollen) composite particles having snowman shapes were prepared by the DSM. With a decrease in the cross-linking density in the composite particles, the volume of the composite particle which was embedded in a spherical styrene phase in the snowman-shaped, styrene-adsorbed particle increased and the contact angle of the styrene phase on the composite particle decreased. In the DSM process, the absorption stage of styrene in the composite particles and the adsorption stage thereon were clearly observed. This suggests that the cross-linking density of the composite particles greatly affects the morphology of the snowman-shaped particles. Received: 13 December 2000 Accepted: 14 March 2001     

Electrically induced and thermally erased properties of side‐chain liquid crystalline polymer/liquid crystal/chiral dopant composites

The properties of synthesized side‐chain liquid crystalline polymer (SCLCP)/liquid crystal (LC)/chiral dopant composites having a chiral nematic (N*) phase at room temperature were investigated by polarized optical microscopy (POM) and a UV/VIS/NIR spectrophotometer. The composite exhibited a planar texture after it was filled into cells under homogeneous boundary conditions and it was transparent. When an electric field was applied to the composite, a focal conic texture was formed and the composite became light scattering. After the electric field was turned off, the light‐scattering state remained stable for some time, i.e. the light‐scattering state exhibited a memory effect. The focal conic texture changed into the planar texture when the composite was heated and the composite became transparent again. Therefore, the composite had electrically induced and thermally erased properties. The SCLCP had some influence on the memory effect and on the thermo‐electro‐optical properties of the composite.     

苯甲酸在疏水性复合电极上的电化学还原行为

以铜片和锌片为基材,复合电镀制得Cu-PTFE(聚四氟乙烯)和Zn-PTFE疏水性复合电极,并将复合电极应用于苯甲酸的电化学还原行为研究。测定了复合电极在电解液中的Tafel极化曲线、循环伏安、电极稳定性和交流阻抗等电化学参数。结果表明,在苯甲酸电还原制备苯甲醛中,Cu-PTFE复合电极相对于Zn-PTFE复合电极具有较高的催化活性,其电还原产率分别为88.4%和79.2%,因此,Cu-PTFE复合电极有望成为苯甲酸电化学还原制备苯甲醛的电极材料。电化学行为的研究结果显示,苯甲酸在疏水性复合电极上的电还原过程可能只受电子迁移过程控制。     

Textile fabricated biodegradable composite stents with core-shell structure

This study proposes composite stents with core–shell structure. Biodegradable polyvinyl alcohol (PVA) yarns are twisted and then coated with polycaprolactone/polyethylene glycol (PEG) blends. The coated yarns are weft knitted into braids and then thermally treated to form composite stents with core–shell structure. The morphological, mechanical, and biological characteristics of the formed composite stents are evaluated to determine the effects of PEG concentration. Results show that composite stents acquire the flexibility of PVA yarns and elasticity of weft knits. The presence of PEG positively influences composite stent performance. When the PEG concentration is 30 wt%, composite stents exhibit a compressive strength of 6.15 N and cell viability of 97.32% after a 24 h of culture. The selected materials are biodegradable, and the novel structure meets the requirements of bioresorbable vascular stent, which suggests that the proposed composite stents have good potential for advancement.     

Viscoelasticity,mechanical properties,and in vivo biocompatibility of injectable polyvinyl alcohol/bioactive glass composite hydrogels as potential bone tissue scaffolds

Abstract

An injectable composite hydrogel composed of polyvinyl alcohol (PVA) and bioactive glass (BG) particles were synthesized by a physical crosslinking approach. The morphology, mechanical properties, and viscoelasticity of the PVA/BG composite hydrogel were characterized. Scanning electronic microscopy (SEM) showed uniform and homogeneous distribution of BG particles throughout the composite hydrogel. The incorporation of 2.5?wt% of BG particles in the composite hydrogel formulations, enhanced the static compressive strength and static elastic modulus by 325% and 150%, respectively. The storage molds (G′) was greater than the loss modules (G′′) at all the frequency range studied, which revealed a self-standing elastic composite hydrogel with a smooth injectability. The PVA/BG composite hydrogel was also implanted subcutaneously in the dorsal region of adult male rats. After 4?weeks of implantation, no inflammatory cells were seen within and around the implant, which indicated that the composite hydrogel was biocompatible. The properties of the synthesized injectable PVA/BG composite hydrogel demonstrate its capability toward bone regeneration.     

复合电沉积的最新研究动态

综述近年来国内外复合电沉积技术最新研究动态.重点探讨纳米复合镀层,电催化复合镀层以及光活性复合镀层等方面的研究现状和发展趋势.纳米复合镀层比一般的复合镀层具有更高的硬度,更好的耐磨性和耐蚀性;电催化复合镀层则可在纯金属电极,合金电极的基础上进一步降低电极反应的过电位.以金属氧化物,导电聚合物作为基质材料的电催化复合镀层已为现代复合电沉积技术开辟了一个新领域.     

The effect of coating on the stiffness and toughness of encapsulated fiber composites

The effect of the coating of the fiber on the stiffness and toughness of composite materials is presented in this paper. The type of composite material considered is of a macroscopically isotropic composite medium containing coated fibers. The models used to simulate such materials consists of: the cylindrical fiber, a cylindrical annulus of the coating, an annulus of the matrix enveloped by an infinite region of an equivalent composite consisting of a transversely isotropic material and representing the real composite with dispersed coated fibers. Solutions for the longitudinal, transverse and shear elastic moduli in the four-phase model were established assuming linear elastic conditions. The results were found to depend on the extent and the mechanical properties of the coating. The stiffness and toughness of the composite were evaluated in models representing plane-stress equatorial sections of the representative volume element of the real material according to the Hashin-Rosen model. The stiffness of the fiber composites was studied by varying the rigidity and the extent of the fiber-coating in the model and evaluating its influence on the overall mechanical behavior of the model. On the other hand, the toughness of the composite was evaluated by the method of caustics in models made of composite PMMA plates with PMMA inclusions coated with a ductile annulus. Interesting results were derived concerning the influence of the soft annulus on the mechanical behavior of the composite.     

Chitosan-based solid electrolyte composite membranes: I. Preparation and characterization

Some chitosan-based solid electrolyte composite membranes were prepared by incorporating potassium hydroxide as the functional ionic source, using glutaraldehyde as cross-linking agent. A three-layer structure with a porous intermediate layer for each composite membrane was observed using SEM. It was found that the concentration of potassium hydroxide solution used to prepare the composite membranes largely influenced the pore volume, porosity, pore size of the intermediate layer, as well as determined the content of potassium hydroxide inside the composite membranes, whereas the degree of cross-linking of composite membrane did not show notable effects. All composite membranes showed significant decreases in both their T_g and onset thermal degradation temperatures with respect to the solid cross-linked chitosan membranes without containing potassium hydroxide. Potassium hydroxide was found to be located inside the intermediate layer of composite membranes with shapes of bulky or fabric crystals. The crystalline properties of matrices of the composite membranes themselves were remarkably modified after being incorporated with potassium hydroxide and main crystalline peaks of matrices almost disappeared for all composite membranes.     

玉米蛋白/吐温-20复合纳米颗粒对姜黄素的包载作用

本文采用反溶剂沉淀法制备了玉米蛋白/吐温-20复合纳米颗粒。通过测定玉米蛋白/吐温-20复合纳米颗粒对姜黄素的包封率、稳定性及荧光光谱性质,考察了不同浓度吐温-20对玉米蛋白/吐温-20复合纳米颗粒包载姜黄素的影响规律。相比玉米蛋白纳米颗粒,玉米蛋白/吐温-20复合纳米颗粒能够显著提高姜黄素的包封率、稳定性、荧光发射光谱强度和各向异性。这些结果说明姜黄素通过疏水作用缔合于玉米蛋白/吐温-20复合纳米颗粒的疏水微区。吐温-20作为稳定剂不仅有助于生成粒径较小的玉米蛋白/吐温-20复合纳米颗粒,而且吐温-20与玉米蛋白的结合能够为姜黄素提供更适合的疏水缔合环境。     

硅藻土负载AgO复合材料的制备及热分解非等温动力学

采用化学氧化沉淀法, 以过硫酸钾为氧化剂制备了硅藻土负载过氧化银(AgO)复合材料, 并使用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和激光粒度仪对其进行了表征, 借助热重(TG)分析研究了复合材料的热分解过程和非等温热分解动力学. 结果表明, 制备的复合材料为正方晶系方英石和单斜晶系AgO混合体, 且AgO质量分数为12.7%; 复合材料的中位径为18.53 μm, 比表面积为203.32 m²/kg, 颗粒的粒度分布在0.614~116.5 μm之间. 复合材料中AgO在171 ℃开始分解成Ag₂O, 在更高温度时Ag₂O进一步分解成Ag; 热分解反应服从以核生成和核成长为控制步骤的A1机理, 其热分解表观活化能为131.37 kJ/mol, 反应频率因子为3.19×10¹³ s^-1. 同自制的AgO粉末相比, 复合材料中AgO的热分解温度升高, 表观活化能上升约40 kJ/mol.     

Cellulose man-made fibre reinforced polypropylene—correlations between fibre and composite properties

A series of viscose fibres from the tyre cord type varying in mechanical parameters and titre were compounded with polypropylene to produce fibre reinforced composites. Single fibre strength is analysed in detail and conclusions are drawn with respect to effective strength values in composite applications. Composites were analysed in terms of tensile and impact properties. Correlations between single fibre and composite properties are studied. High fibre elongation leads to favourable composite impact properties via high composite elongations at break. Using water as a plastisizing agent increasing fibre elongation, notched Charpy impact strength can be improved by more than 50%. Using a modified rule of mixtures and a shear lag model for the composite modulus it was shown how a titre reduction improves the composite stiffness by an increased interfacial area. A direct fibre-composite strength correlation was not found.