聚合物纳米杂化高性能光功能材料

近年来材料科学与技术的不断发展,对光学材料提出了高性能化和多功能化的需求,为此,研究者们结合传统有机聚合物光学材料和无机光学材料的优势,提出了备受关注的聚合物纳米粒子杂化的策略.本文首先概述了针对杂化材料透光性进行控制的杂化方法,指出杂化方法的选择很大程度上与材料性质尤其是纳米相的性质相关,而杂化方法的目的则在于实现纳米杂化材料的透光性控制,纳米杂化光功能材料实现功能的前提即为透光性.随后,分别介绍了聚合物纳米杂化策略在高折射率材料与发光材料中的应用.对于高折射率材料,总结了提升材料折射率的不同策略.对于发光材料,总结了基于聚合物相和纳米相之间不同的相互作用而采用各种杂化方式以及相关的性能提升.接下来,讨论了聚合物纳米杂化光功能材料在光学和机械、热学、表面性能方面的调控手段和性能提升的策略.最后,提出了下一代光学杂化材料所面临的困难与挑战,以进一步推动这一领域的发展.     

高折射率聚合物-无机纳米光学杂化材料的设计与制备及其应用

传统的高折射率聚合物光学材料,可以通过向聚合物中引入一些芳香环,含硫基团以及除氟以外的其他卤素原子来提高聚合物光学材料的折射率,但是就目前的研究现状来看,这类纯聚合物光学材料的折射率一般都低于1.8.而将具有高折射率的无机纳米粒子引入到聚合物中,所制备的聚合物-无机纳米光学材料的折射率能够达到1.8以上.而且这类高折射率聚合物-无机纳米光学杂化材料同时具有高分子光学材料和无机材料的双重优点,具有广泛的应用前景.鉴于当前高折射率聚合物-无机纳米光学杂化材料发展之迅速和其研究与开发的重要性,并结合目前国内外的研究现状,本文就高折射率聚合物-无机纳米光学杂化材料的设计、制备方法及其相关应用做一个比较系统的介绍,同时对这类材料在未来研究中所应注意的问题也提出了相应的看法.     

Cd基化合物纳米晶-有机聚合物杂化太阳能电池研究进展

有机-无机杂化太阳能电池因其结合了有机材料和无机材料各自的优势而引起了人们的广泛关注和研究. Cd基化合物纳米晶因其具有制备方法简单、尺寸及形貌可控、载流子迁移率高和稳定性好等优点而成为最早被研究的一类无机受体. 本文介绍了有机-无机杂化太阳能电池的结构及原理, 分析了影响有机-无机杂化太阳能电池效率的三个主要因素, 分别是开路电压(V_oc)、短路电流(J_sc)和填充因子(FF). 从改善Cd基化合物纳米晶的合成方法, 增加Cd基化合物纳米晶和有机聚合物间的界面接触, 以及优化Cd基化合物纳米晶和有机聚合物所用溶剂和所占比例等方面阐述了近年来Cd基化合物纳米晶-有机聚合物杂化太阳能电池的研究进展. 并展望了Cd基化合物纳米晶-有机聚合物杂化太阳能电池的发展方向.     

聚合物纳米杂化材料的控制合成、自组装及功能化

聚合物纳米杂化材料的制备及功能化是当前国际前沿研究课题之一.特殊结构的聚合物可以通过分子间特殊相互作用,在纳米尺度上自发地组装成具有特殊结构和形态的集合体,这类材料在新材料、电子以及生物医学等领域具有广泛的应用前景.本文介绍国内外,特别是厦门大学在双亲性分子及嵌段共聚物的模板自组装、基于POSS单体纳米构筑单元以及POSS嵌段聚合物自组装的有机/无机纳米杂化材料、模板控制导电高分子材料纳米形态构筑等领域材料的可控合成和组装,与此同时对相关材料的性能及功能化应用进行了简要的讨论.     

凹凸棒石:从矿物材料到功能材料

凹凸棒石(attapulgite)是一种天然的一维纳米级含水富镁铝硅酸盐黏土矿物,具有纳米棒状晶体结构、纳米孔道和表面活性基团,作为重要的基础材料在农业、化工、环保、吸附分离和复合材料等领域得到了广泛应用.近年来,凹凸棒石纳米化技术取得快速发展,天然凹凸棒石矿物中的棒晶束或聚集体得以高效解离成单分散的纳米棒晶,同时保留了硅酸盐黏土矿物的环境友好特性,实现了黏土矿物材料向纳米材料的转变.凹凸棒石集纳米棒晶和纳米孔道于一体的独特结构,使其既可以通过棒晶和表面基团构筑纳米复合材料,也可以通过其纳米孔道构筑杂化功能材料.因此,凹凸棒石成为构筑形形色色功能材料的"新宠",实现了黏土矿物材料的纳米功能化应用.本文在介绍凹凸棒石晶体结构及理化性质的基础上,重点综述了凹凸棒石棒晶束解离纳米化、结构调控和新型功能材料构筑(吸附材料、胶体材料、杂化材料、聚合物复合材料、仿生涂层、催化和能源材料)等方面的最新研究进展,并展望了凹凸棒石研究与功能化应用的发展前景,旨在为凹凸棒石乃至其他黏土矿物及其功能材料的研究起到抛砖引玉的作用.     

纳米AgBr/PMMA光致变色杂化材料制备与表征

采用本体聚合法制备了纳米AgBr/PMMA(聚甲基丙烯酸甲酯)光致变色杂化材料. XRD分析表明，纳米AgBr/PMMA杂化材料是无定形的. SEM分析表明， AgBr含量不同，杂化材料的断面形貌明显不同，随AgBr含量的增加，杂化材料由韧性断裂向脆性断裂转变. EDS面分析表明， Ag、Br元素在杂化材料中均匀分布.所制备的纳米AgBr/PMMA杂化材料具有一定的光致变色效应.     

纳米CeO_2/PMMA杂化材料的制备与表征

采用在位分散聚合法制备了纳米CeO2 /PMMA杂化材料.XRD分析表明,杂化材料是无定形的.SEM分析表明,杂化材料中CeO2 含量不同,材料的断面形貌明显不同,随CeO2 含量的增加,杂化材料由韧性断裂向脆性断裂转变.EDS面分析表明,Ce在杂化材料中分布均匀.实验表明,随CeO2 含量的增加,杂化材料的透过率和溶解性降低     

石墨炔纳米材料的制备及在电化学能源中的应用

石墨炔纳米材料的制备与应用是石墨炔材料研究的重要方向, 通过对其纳米结构进行设计与优化, 可以提高石墨炔材料及其杂化结构的性能, 拓展其在能源储存与转换领域的应用. 本综述介绍了不同形貌和结构的石墨炔基纳米材料, 如纳米墙、 纳米片、 纳米薄膜等结构. 阐述了不同结构特征的石墨炔基纳米材料在电化学储能器件以及电化学能源催化中的应用, 同时也探讨了石墨炔不同纳米形貌和结构在能源应用领域快速发展的机遇及所面临的挑战.     

可聚合纳米无机氧化物杂化材料的制备及其在紫外光固化涂料中的应用

可聚合纳米无机氧化物杂化材料在紫外光固化涂料中具有较好的分散性能.与涂料中的单体和预聚物进行光聚合形成有机/无机杂化网络结构的聚合物,从而提高涂料固化膜的热稳定性能、硬度和耐磨性能等,在紫外光固化涂料的制备方面有着广阔的应用前景.目前,该类杂化材料主要采用硅烷偶联剂改性、化学接枝改性和溶胶一凝胶方法制备.本文就可聚合纳...     

荧光纳米晶制备及其与聚合物的复合组装

纳米尺寸无机晶体(纳米晶)具有特殊的光、电和磁等性能, 但这类材料通常以胶体溶液或固体粉末的状态存在, 稳定性和分散性较差. 实现这类材料的应用, 需要将其与一些惰性介质复合, 从而提高稳定性和加工性. 聚合物材料作为一种有机惰性介质, 具有良好的材料兼容性和可加工性, 是稳定纳米晶材料的首选介质. 此外, 很多聚合物材料本身也具备特殊的性能, 可以对纳米晶性能进行有益的补充和调节. 因此, 功能纳米晶材料与聚合物复合, 将成为开启材料性能宝库的钥匙. 我们研究组结合自己的相关研究, 系统总结了荧光纳米晶材料与聚合物的复合组装方法, 着重阐述不同方法的优势及意义, 希望对从事这一前沿领域研究的人们有所启发.     

高折射率有机/无机纳米杂化透明膜层材料的制备与性质研究

采用溶胶-凝胶法,将钛酸酯和硅烷偶联剂(KH-560)进行共水解,经涂膜、固化,制备了一系列含有无机二氧化钛纳米相的无机/有机杂化膜层材料,通过不同方法对杂化膜层的微结构、光学、机械和热性质进行了表征.结果表明,所得到的有机/无机纳米复合膜层,在可见光范围内的透过率均在90%以上,同时具有较好的耐热性和较高的折射率(nd=1.47~1.73),并且膜层与基材的附着性好,铅笔硬度达到4~5H.     

Composites of hydrophilic polymers and organic nanocrystals enable enhanced robustness

We describe a new family of composite materials, polymer/organic nanocrystal (ONC) hybrids. These were prepared from soluble ONCs based on perylene diimides (PDI) and water‐soluble polymers (sodium alginate and polyvinyl alcohol). Polymer/ONC films were characterized by optical spectroscopy, electron microscopy, and tensile strength studies. The films show enhanced chemical and mechanical stability due to synergy between the constituents. The hybrid films are stable in both water and organic solvents, unlike the individual components. The ONCs we employed possess nonlinear optical activity (second harmonic generation, SHG); they showed improved photostability (stable SHG under laser light) in the hybrids. Tensile strength enhancement (as high as twofold in the film having just 2.4% ONCs by weight) was observed as revealed by mechanical measurements. Hybrids with aligned ONCs were also prepared using simple extrusion via syringe needle followed by gelation. Employing ONCs in polymeric hybrid materials enables facile fabrication in aqueous media, synergy, chemical, mechanical, and photostability as well as useful photofunction (SHG), introducing a versatile class of composite materials.     

碲化镉纳米晶与聚合物复合研究进展

综述了近年来半导体纳米晶CdTe/聚合物复合材料在电致发光器件和复合发光材料方面的研究和应用进展情况,详细介绍了CdTe与水溶性高分子,非水溶性高分子以及生物大分子的复合情况,并展望了其发展前景。     

Organic nanocrystals grown in sol-gel matrices: new hybrid organic-inorganic materials for optics

We have developed a simple and generic preparation of stable organic nanocry stals grown in gel-glass matrices. The synthesis of these hybrid organic-inorganic materials is based on the confined nucleation and growth of organic phases in the pores of dense gels. For bulk nanocomposite samples, narrow size distributions of particles (10–20 nm in diameter) are obtained. We have extended this method to the preparation of organic nanocrystals embedded in sol-gel thin films prepared by spin-coating. For all these nanocomposite materials, we have significantly increased the dye stability and obtained promising optical properties: luminescence, non-linear optical properties or photochromism. Moreover, we have also demonstrated basic working principles of a new type of fluorescent nanosensor through the preparation of organic luminescent nanocrystals grown in silicate films.     

Mussel-inspired fabrication of encoded polymer films for electrochemical identification

Encoded polymer films for electrochemical identification have been achieved by embedding different semiconductor nanocrystals into self-polymerized dopamine films. Such encoded polydopamine films based on mussel-inspired surface chemistry show high adhesive ability and can be created on a wide range of inorganic and organic materials, including noble metals, oxides, ceramics, and synthetic polymers. By incorporating different predetermined levels of various redox nanomarkers, the use of multi-film system composed of multiple, sequenced polydopamine identification films could theoretically generate nearly unlimited (>10¹²) distinct voltammetric signatures (electric codes).     

聚合物主体中纳米CdTe的光致发光与电致发光性质

利用紫外和荧光光谱技术研究了共轭聚合物PPE4+分别在溶液和薄膜中与纳晶CdTe间的能量传递现象。通过静电层层组装技术制备了混杂有纳晶CdTe的PPE4+薄膜发光二极管,并测试了其电致发光性质。结果表明在溶液和薄膜中共轭聚合物PPE4+与纳晶CdTe间均能发生有效的能量转移,而共轭聚合物PPE4+在能量传递过程中起到分子天线的作用。     

Control of the optical properties of CdTe nanocrystals by selective exchange of Te with thiolate: effect of organic ligands on the formation of core-shell structures

Changes in the optical properties of CdTe nanocrystals through selective surface exchange reaction with thiolate molecules in the organic phase are studied with an aim to investigate the mechanism and the role of organic ligands. The reaction was mediated by dissociation of Te anions via oxidation in air from CdTe nanocrystals, followed by attachment of thiolate molecules in a 1:1 stoichiometric manner. This results in a gradual shell formation and a corresponding decrease in the size of the fluorescent CdTe cores, which induces a blue shift of both the absorption edge and emission wavelength in the visible region. A systematic study including the addition of ligands at different concentrations revealed that Te dissociation is the rate-determining step for the process and the degree of blue shift is significantly dependent on the amount of organic ligands present. The process could also be kinetically controlled through the addition of an excess amount of thiolate ligands, allowing systematic tuning of the emission properties of nanocrystals under ambient conditions.     

Highly sensitive detection of transient absorption in dye-doped ultrathin polymer films by the TiO(2)/K(+) composite optical waveguide method upon pulsed laser excitation

A composite optical waveguide (OWG) composed of a 10–18 nm thick titanium dioxide (TiO₂) film sputtered on a conventional K⁺-doped optical waveguide was first applied to detect transient absorption of organic dyes in ultrathin polymer films upon excitation with ns laser. The thickness of the TiO₂ film considerably affected the relative sensitivity of the composite OWG. The composite OWG with 10 nm thick TiO₂ gave much stronger transient absorption for 30–415 nm thick polymer films containing organic dyes than that with 18 nm TiO₂. Transient absorption of phthalocyanine and spiropyran in 20–135 nm thick polymer films was detected 3–20 times more sensitively by the composite OWG with 10 nm TiO₂ than the conventional K⁺-doped OWG which showed a 150-fold sensitivity as compared with the usual normal incidence method. The relative sensitivity of the composite waveguide was also affected by the thickness and refractive index of polymers.     

Distribution of Zinc Oxide Nanocrystals in a Polymer Film

The structure of polymer films modified with zinc oxide nanocrystals was studied by the optical absorption and small-angle X-ray scattering methods. Small-angle X-ray scattering allows determination of the nanoparticle size distribution function, which is the decisive factor in predicting the optical properties of heterophase materials, including filled polymer films. The optical absorption spectrum of an acrylate polymer film doped with 1.6 wt % zinc oxide nanocrystals approaches the ideal absorber spectrum, which allows this material to be recommended for use as a protective color filter.