掺Eu及Ag微粒的SiO2凝胶在多孔阳极氧化铝中的荧光增强

近年来,将稀土配合物掺杂于溶胶－凝胶（Sol-gel)基质中及在溶胶－凝胶制备过程中原位（In stitu)合成稀土配合物已有报道^[1]。溶胶－凝胶基质使掺杂分子和外界隔绝,形成一种很好的保护基质,而渗杂的光活性物质,由于受到笼效应的影响,掺杂分子之间相互孤立,减小了聚集体的生成和浓度猝灭^[2]。在溶胶－凝胶中掺杂镧系离子,尤其掺杂Eu^2 和Sm^2 等二价离子已成为研究热点,它们在光学存储^[3]、固态激光^[4]、绿光发光材料、药物学上的X射线无机发光材料等方面具有潜在应用前景。二价镧系离子（如Eu^2 ）通常是由三价离子（Eu^3 ）在加热条件下,经短波光还原或电化学还原产生的,而在溶胶－凝胶中既可有效地还原Eu^3 ,也可将Eu^2 固定在光学透明凝胶中^[5]。国内有关凝胶中掺杂稀土离子的荧光现象虽报道很多^[6],但将凝胶固定在多孔基底上却未见报道。多孔阳极氧化铝具有规则的六边形孔状结构,还可以根据需要制成不同的形状,在其为模板制备金纳米线^[7],由于溶胶可渗入几个至十个纳米深的孔道中,在多孔基底上用溶胶－凝胶法制作的薄膜能增强荧光现象并没有较好的重现性。     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

自蔓燃工艺制备纳米TiO2降解制药废水的研究

目前已报道的制备纳米二氧化钛的方法有气相氧化法[1,2]、水热法[1,3]和溶胶-凝胶(sol-gel)法[1,4,5]等。这些方法均以有机钛盐或无机钛盐为原料,制备成本高,不利于在废水处理中作光催化剂推广使用。溶胶—凝胶自蔓燃法(简称SAS)也称低温燃烧合成法,由于工艺简单、反应条件易于     

无机物的光学和电化学传感器

本文讨论将溶胶凝胶作为一种基质来发展独特的传感策略．溶胶凝胶为传感基质的制备和发展提供了无限空间,这种空间得益于基质物理性质的多样性,可以通过改变一些传感器已知的制备条件和合成技术来实现．我们在对传感需求的认真考虑和研究的基础上,开发出了用于一些分析物的新的检测方法,同时发展了它们的应用．溶胶凝胶被用来监测浓强酸（[H^＋]=1～11M）,浓强碱（[OH^-]：1～10M）及采用双传感方法来测定混合溶剂／溶质系统．本文还讨论了使用配体嫁接的块状溶胶凝胶对金属离子进行光学测定．最后介绍了用电化学法和溶胶凝胶修饰的电极来测定六价铬的方法．     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶－凝胶技术制备无机催化膜，该方法的基本原理是利用合适的金属配合物在胶粒表面吸附作用，经溶胶－凝胶过程，将活性组分结合到无机膜中，实验测定结果表明：（ＮｉＥＤＴＡ）＾２－，ＶＯ＾－３，ＭｏＯ＾２－４，（Ｐｄ（ＮＨ３）４＾２＋，ＰｄＣｌ＾２－４，ＰｔＣｌ＾２－６和ＲｈＣｌ＾３－６可用来修饰ＡｌＯＯＨ溶胶，以Ｐｄ／γ－Ａｌ２Ｏ３催化膜的制备为例，经三次溶胶－凝胶过程，     

3-氨丙基三乙氧基硅烷对溶胶-凝胶法苯乙烯-顺丁烯二酸酐共聚物/SiO_2杂化材料的制备与性能的影响

用３ 氨丙基三乙氧基硅烷（ＡＰＴＥＳ）作为偶联剂，通过溶胶 凝胶（Ｓｏｌ Ｇｅｌ）过程制得两相以共价键结合的透明苯乙烯 顺丁烯二酸酐共聚物／ＳｉＯ２杂化材料．通过ＦＴＩＲ分析等证实了材料有机相与无机相间是以共价键结合的．分析了材料热处理温度和分别用盐酸或氨水作催化剂时对材料溶胶分数的影响、偶联剂及其用量对溶胶 凝胶体系凝胶时间的影响、并研究了杂化材料中无机含量对材料折射率和Ｔｇ的影响     

自然光照下PEG/PAA 凝胶在Fe3+/CA溶液中的 凝胶-溶胶转化行为的研究

本文将PEG/PAA凝胶浸入铁/柠檬酸（Fe3+/CA）溶液中,在自然光照一定的时间可实现凝胶-溶胶的相互转化,而且转化行为受溶液的组成及其pH值的影响。只有当溶液中[Fe3 ]0: [CA]0≤1:2,且溶液的pH在1-6之间,该转化才会发生,通过改变溶液中[Fe3 ]0: [CA]0的值或溶液的pH可以有效地控制其转化速率。此外,实验结果表明,当凝胶转化为溶胶后,在其中加入高价金属阳离子,例如Fe3 、 Al3 、Ce4 、Cu2 等,溶胶又会再次转化为凝胶。由于这种新颖的特性,该凝胶有望应用于药物释放、细胞培养等领域。     

Sol-Gel技术制备二阶有机/无机复合非线性光学材料的研究进展

溶胶－凝胶技术是制备材料的一种新兴低温工艺，它为两种完全不相容的成份—聚合物材料和无机玻璃的大比例混合（或键合）创造了可能，使得制备出的材料兼备两种成份的优点。本文综述了近年来溶胶－凝胶技术在制备有机／无机复合非线性光学材料领域中的应用，并简要分析了当前研究工作所面临的问题。     

基于溶胶-凝壳聚糖/SiO2杂化材料的安培型葡萄糖生物传感器

近年来 ,基于溶胶 -凝胶技术的有机 /无机杂化复合材料由于具有有机物的柔性和易修饰性 ,以及无机物的刚性和稳定性等 ,因此有利于保持生物分子的活性和生物传感器的研制 [1] .壳聚糖 ( CS)具有易成膜性和生物相容性 ,其在生物传感器中的研究已受到重视 [2 ] .本文通过原位溶胶 -凝胶 ( Sol- gel)技术 ,用 CS和甲基三甲氧基硅烷 ( MTOS)制备了 CS/Si O2 有机 /无机杂化材料 ,并将其用于对葡萄糖氧化酶 ( GOD)的固定 ,研制出葡萄糖生物传感器 .采用人工过氧化物酶普鲁士蓝 ( PB) [3]作为电子传递的媒介体 ,并外加一层 Nafion膜以增强…     

3—氨丙基三乙氧基硅烷对溶胶—凝胶法苯乙烯—顺丁烯二酸酐共聚物／Sio2杂化

用３－氨丙基三乙氧基硅烷（ＡＰＴＥＳ）作为偶联剂，通过溶胶－凝胶（ｓｏｌ－Ｇｅｌ）过程制得两相以共价键结合的透明苯乙烯－顺丁烯二酸酐共聚物／ＳｉＯ２杂化材料。通过ＦＴＩＲ分析等证实了材料有机相与无相相间是以共价键结合的。分析了材料热处理温度和分别用盐酸或氨水作催化剂时对材料溶胶分数的影响、偶联剂及其用量对溶胶－凝胶体系凝胶时间的影响、并研究了杂化材料中无机含量对材料折射率和Ｔｇ的影响。     

PMMA-ZrO2等有机无机杂化材料的制备与表征

以烯丙基乙酰丙酮作为偶闻剂应秀溶胶凝胶法制备了一系列均匀透明的ＰＭＭＡ－ＺｒＯ２等有机无机杂化材料，利用ＵＶ，ＩＲ对其制备过程进行了研究，并测定了所得杂化玻璃的ＴＧＡ性质。     

High Refractive Index Films Prepared from Titanium Chloride and Methyl Methacrylate via a Non-Aqueous Sol–Gel Route

Poly(methylmethacrylate)/silica/titania films were prepared via a nonaqueous sol–gel route at ambient temperature, followed by spin-coating and multistep baking. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). Silicic acid and titanium(IV) chloride were used as the precursors of the inorganic component. FTIR results indicated the successful bonding between TiO₂ and SiO₂. TEM images suggested the silica/titania particles were well dispersed in the Poly(methyl methacrylate) (PMMA) matrix with the particles size smaller than 40 nm in our study. The refractive index and extinction coefficient were also studied. The refractive index of the hybrid increased with increasing the titania content, and the hybrid films showed high optical transparency in visible region.     

聚甲基丙烯酸甲酯/二氧化硅杂化材料制备与性能

溶胶-凝胶;聚硅酸;聚甲基丙烯酸甲酯/二氧化硅杂化材料制备与性能     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

丙烯酸羟乙酯对丙烯酸酯改性水性聚氨酯性能的影响

以异佛尔酮二异氰酸酯、二羟甲基丙酸和聚丙醚二醇等为聚氨酯原料, 丙烯酸丁酯、甲基丙烯酸甲酯、三羟甲基丙烷三丙烯酸酯为丙烯酸酯类单体, 丙烯酸羟乙酯(HEA)为聚氨酯和聚丙烯酸酯间的偶联剂合成了丙烯酸酯改性水性聚氨酯(PU-AC)乳液. 首先建立并验证了一种测定PU接枝率, 即PU与丙烯酸酯发生接枝的部分占PU总数的百分比的方法, 然后探讨了加入HEA后的反应温度和HEA用量对PU接枝率、PU-AC乳胶粒径、胶膜吸水率和交联度等性能的影响. 随着HEA与PU预聚体反应温度和HEA用量的提高, 体系中的最终残余NCO逐渐降低. 当HEA用量低于其加入前体系中残余NCO量时, 增加其用量使PU接枝率和PU-AC乳胶粒径逐渐增加; 当HEA用量大于体系残余的NCO量后继续增加其用量对PU接枝率和PU-AC乳胶粒径的影响不大. 胶膜吸水率随着HEA用量的增加而降低.     

Incorporation of titanium dioxide particles into polymer matrix using block copolymer micelles for fabrication of high refractive and transparent organic–inorganic hybrid materials

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles into poly(methyl methacrylate) (PMMA) to exploit high refractive and transparent organic–inorganic hybrid materials. Formation of TiO₂ particles of around 20 nm was conducted within hydrophilic core of block copolymer micelles of poly(methyl methacrylate‐block‐acrylic acid) (PMMA‐b‐PAA) in toluene via sol–gel process from titanium isopropoxide and hydrochloric acid. Subsequently, incorporation of TiO₂ particles into PMMA matrix was carried out by casting toluene solution of TiO₂ precursor‐loaded copolymer micelles, prepared from PMMA₃₅₀‐b‐PAA₉₃ and the precursor of mole ratio Ti⁴⁺/carboxyl 4.0, and PMMA. Hybrid films of TiO₂/PMMA exhibited high transparency to achieve transmission over 87% at 500 nm at 30 wt % of TiO₂ content. The refractive index of resulting hybrid films at 633 nm linearly increased with TiO₂ content to attain 1.579 at 30 wt % TiO₂, which was 0.1 higher than that of PMMA. Cross‐sectional transmission electron microscope images of TiO₂/PMMA hybrid films showed existence of TiO₂ clusters less than 100 nm, which were probably formed by aggregation or agglutination of TiO₂ particles during a drying process. It was also observed that decomposition temperature of the hybrid films elevated with increasing TiO₂ content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Molecular mobility in hybrid materials: A study of the 3(Trimethoxysilyl) propyl methacrylate-methyl methacrylate system

Hybrid glasses based on 3(Trimethoxysilyl) propyl methacrylate (TMSM) and methyl methacrylate (MMA) were successfully prepared by sol-gel process. The molecular mobility of hybrid materials was studied by mean of high resolution dynamic mechanical spectrometry technique. The results of hybrid materials were compared with those of polymethylmethacrylate (PMMA) prepared in the same conditions and interpreted in term of local or large-scale molecular motion.     

Synthesis of telechelics and block copolymers via “living” radical polymerization

Hydroxy‐telechelic poly(methyl methacrylate)s of molecular weights below 5000 were obtained by atom transfer radical polymerization (ATRP) of methyl methacrylate followed by end‐capping with allyl alcohol via atom transfer radical addition (ATRA). As initiators for the ATRP, monofunctional initiators with an additional hydroxy group in the molecule or bifunctional initiators were employed. The successful synthesis of the hydroxy‐telechelic PMMA was proved by determination of their molecular weight using MALDI‐TOF‐MS. The efficiency of the end‐capping reaction was determined by ¹H NMR spectroscopy using the allyl N‐(4‐tolyl)carbamate as end‐capping agent. Block copolymers comprising a poly(ethylene oxide) (PEO) block and a poly(methyl methacrylate) (PMMA) block were prepared by ATRP using a macroinitiator on the PEO basis. The dormant species of the macroinitiator consists of the phenyl chloroacetate moiety which shows a high rate of initiation. The successful synthesis of the poly(ethylene oxide)‐block‐poly(methyl methacrylate) was proved by ¹H NMR spectroscopy; the ratios of EO/MMA repeating units in the feed and the copolymer were nearly equal.     

Photophysical properties of ternary hybrid system of lanthanide center linking organically modified silica and polymeric chain

According to coordination chemistry principle and molecular assembly technology, series of ternary lanthanide centered hybrid systems have been constructed through coordination bonds. Among one component (ligand) is organically modified Si-O network, which originates from the functional molecular bridge (BFPPSi) by the functionalization of 1,3-bis(2-formylphenoxy)-2-propanol (BFPP) with 3-(triethoxysilyl)propyl isocyanate. In the second component (ligand), three different organic polymeric chains are introduced, poly-(methyl methacrylate) (PMMA, from the polymerization of MMA with the benzoyl peroxide [BPO] as the initiator), poly-(methyl acrylic acid) (PMAA, from the polymerization of MAA with the BPO as the initiator), polyvinyl pyridine, respectively. All these ternary hybrid materials show homogeneous, regular microstructure, suggesting the existence of assembly process of lanthanide centers, inorganic Si-O network and organic polymer chain. Compared to the binary hybrids without polymer chain, the photoluminescent properties of these ternary hybrids present stronger luminescent intensities, longer lifetimes and higher luminescent quantum efficiencies indicating that the introduction of organic polymer chain is favorable for the luminescence of the whole hybrid systems.     

Synthesis of Poly (methyl methacrylate)/Zinc Oxide Nanocomposite with Core-Shell Morphology by Atom Transfer Radical Polymerization

A method to prepare zinc oxide (ZnO) nanoparticles with a covalently bonded poly(methyl methacrylate) (PMMA) shell by surface initiated atom transfer radical polymerization (ATRP) was reported. First, the initiator for ATRP was covalently bonded onto the surface of zinc oxide nanoparticles through our novel method. Firstly, the surface of ZnO nanoparticle was treated with 3-aminopropyl triethoxysilane, a silane coupling agent, and then this functionalization nanoparticle was reacted with α-chloro phenyl acetyl chloride to prepare atom transfer radical polymerization macroinitiator. The metal-catalyzed radical polymerization of MMA with ZnOmacroinitiator was performed using a copper catalyst system to give the ZnO-based nanoparticles hybrids linking PMMA segments (poly (methyl methacrylate)/zinc oxide nanocomposite). These hybrid nanoparticles had an exceptionally good dispersability in organic solvents and were subjected to detailed characterization using FTIR, TEM and TGA and DSC analyzed.