聚硅氧烷基纳米多孔薄膜双分形结构的同步辐射小角X射线散射分析

以聚硅氧烷基材料为预聚体,采用两种核壳型致孔剂,以旋涂工艺分别制备两组聚硅氧烷基纳米多孔薄膜,采用北京同步辐射装置(BSRF)光源进行了小角X射线散射测试,在掠入射模式(入射角αi=0.2°)下得到了两组不同孔隙率纳米多孔薄膜的二维散射数据,在此基础上分析了薄膜的分形特征,发现所制备的薄膜除试样A1外,均存在双分形结构...     

纳米多孔薄膜孔结构的非破坏性表征

对纳米多孔低介电常数薄膜孔洞率、孔径、孔径分布和孔洞连通性等孔结构的表征有助于理解薄膜的结构和提高其性能。近年来开展了利用与特殊X射线反射联用的小角中子散射、小角X 射线散射、椭偏测孔仪、正电子湮没谱和表面声波谱等非破坏性方法表征多孔低介电常数薄膜孔结构的研究。介绍了这些方法的基本原理,综述了利用这些方法研究低介电常数介质薄膜及其集成工艺的进展,总结了这些方法表征多孔薄膜孔结构的特征。     

多孔TiO2纳米纤维的制备及其对染料废水的光催化降解性能研究

以钛酸四正丁酯(TBT)为原料,结合溶胶-凝胶、静电纺丝和高温炭化的技术与原理,制得实心二氧化钛(TiO_2)纳米纤维,并通过添加不同含量的致孔剂偶氮二甲酸二异丙酯(DIPA)制得多孔TiO_2纳米纤维。并对多孔TiO_2纳米纤维的形貌与晶型结构进行了表征与分析。研究结果表明,经煅烧后制得的实心和多孔TiO_2纳米纤维分别为金红石型和锐钛矿型结构;在DIPA用量为5%(wt,质量分数)制得的多孔TiO_2纳米纤维用量50mg,在50mL亚甲基蓝溶液,光照3h条件下,对亚甲基蓝溶液的降解率最高达到91.5%。     

去合金化制备孔径可控纳米多孔金属研究进展

纳米多孔金属具有三维连通、双连续的纳米级孔结构,使其具有超高比表面积、高强度、低密度等独特理化性能,在力学、催化、传感、拉曼散射等领域具有广阔的应用前景,而且纳米多孔金属的性能表现出一定的尺寸效应,因此研究孔结构调控对纳米多孔金属的实际应用具有重要意义。目前,去合金化制备孔径可控的纳米多孔金属主要集中在调节去合金化工艺(腐蚀方式、腐蚀温度、腐蚀电解质、腐蚀添加剂等)和去合金化后处理过程(热处理粗化、溶液浸泡)两方面,探索纳米多孔金属在不同工艺条件下孔结构的成孔机制、孔结构演变规律为制备孔结构呈特征规律分布(如梯度分布、分级分布、均匀分布)的纳米多孔金属块材或薄膜奠定了夯实的基础。     

介孔碳材料对染料大分子的吸附性能研究

采用嵌段共聚物聚氧乙烯-聚氧丙烯-聚氧乙烯(PEO-PPO-PEO,F127)和聚二甲基硅氧烷-聚氧乙烯(PDMS-PEO)为混合模板剂制备了有序介孔碳材料,并采用小角X射线散射(SAXS)和氮气吸附/脱附对其结构进行了表征,进一步研究了上述介孔碳材料对甲基橙、亚甲基蓝和碱性品红3种染料大分子的吸附性能。     

含氟聚合物纳米多孔纳米纤维膜的制备

采用"电纺-相分离-沥滤"方法制备了聚(偏氟乙烯-co-六氟丙烯)(PVDF-HFP)以及聚偏氟乙烯(PVDF)纳米多孔纳米纤维膜.首先,将PVDF-HFP或PVDF和致孔剂聚乙烯吡咯烷酮(PVP)混合电纺,得到共混物纳米纤维膜.然后,将纳米纤维膜在水中沥洗出共混物中的PVP,获得纳米多孔纳米纤维膜.用场发射扫描电子显微镜(FESEM)观察水洗前后纤维表面精细结构.结果表明,纳米多孔纳米纤维表面呈多孔结构,孔径数10 nm.PVP的分子量对水洗后纤维表面结构有明显影响.致孔剂含量不同获得的PVDF-HFP纳米多孔纤维膜力学性能相近.     

利用表面活性剂量改变孔洞率制备的纳米多孔SiO2膜

采用表面活性剂十六烷基三甲基溴化氨(CTAB)为模板剂,在酸性条件下产生多孔结构,再经热处理去除CTAB。实验中使用溶胶?凝胶技术,正硅酸乙酯(TEOS)为硅源,以及二次去离子水,盐酸为催化剂等原料,利用表面活性剂与硅源水解后形成的聚集体相互作用,在溶液中形成分子自组装体,制备前驱体溶胶。通过简单提拉迅速蒸发溶剂制备纳米多孔或纳米介孔SiO2薄膜,分析和研究了表面活性剂浓度对纳米多孔SiO2薄膜的结构和孔洞率的影响,通过操纵表面活性剂的含量,能控制薄膜的纳米结构、孔洞率、孔大小和孔的形态以及膜的形貌。小角度射线衍射、场发射透射电子显微镜、原子力显微镜显示可以制得具有六方、立方和由三维六方和简单立方组成的新相结构以及比介孔大的纳米多孔结构的薄膜。椭偏仪测量得到所制备薄膜的孔洞率为51.8%-65.6%,借助此孔洞率能计算薄膜的折射率和介电常数。     

掠射角溅射沉积纳米结构氧化钨薄膜

采用掠射角反应磁控溅射法在室温下沉积了纳米结构氧化钨(WO₃)薄膜, 并对薄膜进行热处理。利用场发射扫描电镜(FE-SEM)和X射线衍射仪(XRD)对氧化钨薄膜的形貌和结构进行了表征。当掠射角度为80°时, 采用直流电源沉积的氧化钨薄膜具有纳米斜柱状结构, 而采用脉冲直流电源沉积的薄膜呈现纳米孔结构。纳米薄膜经450℃热处理3 h后, 纳米斜柱彼此连接, 失去规整结构, 而纳米孔结构的孔尺寸变大。XRD分析表明室温沉积的氧化钨薄膜具有无定形结构, 经450℃热处理1 h后, 转变为单斜晶相。具有纳米斜柱状或纳米孔结构氧化钨薄膜的光学调制幅度在波长600 nm时达到60%, 且电致变色性能可逆。     

全氟离子膜纳米结构演变的研究进展

简述了全氟离子膜微观结构模型的研究进展，以此展开了对于全氟离子膜纳米结构研究，并详细阐述了全氟离子膜纳米结构演变的研究进展及纳米结构与离子膜离子传输能力的相关性分析.贯穿整个研究进展最重要的是微观表征技术的应用，这些技术包括广角X射线散射(Wide-Angle X-ray Scattering, WAXS)、小角X射线散射(Small-Angle X-ray Scattering, SAXS)和小角中子散射(Small-Angle Neutron Scattering, SANS),以此为基础讨论了吸水率、温度、预处理等对全氟离子膜的纳米结构的影响.     

低介电常数多孔二氧化硅薄膜的制备与研究

本文报道了一种新型纳米多孔低介电常数薄膜的制备方法.以十六烷基三甲基溴化铵(CTAB)为模板剂,正硅酸乙酯为硅源,盐酸为催化剂,采用溶胶-凝胶技术,通过提拉法制备了二氧化硅透明介孔薄膜.用红外光谱、小角XRD、原子力显微镜对样品进行了表征,并采用椭偏仪和阻抗分析仪测量薄膜的折射率和介电常数.通过调节表面活性剂浓度和老化时间等实验条件制备出了K＜2.5、机械强度好的低介电常数薄膜.     

Preparation of nanoporous poly(methyl silsesquioxanes) films using PS-b-P4VP as template

Nanoporous poly(methyl silsesquioxane) (PMSSQ) film was prepared through the templating of an amphiphilic block copolymer, poly(styrene-4-vinyl pyridine) (PS-b-P4VP). The experimental and theoretical studies suggest that the intermolecular hydrogen bonding is existed between the PMSSQ precursor and PS-b-P4VP. The miscible hybrid and the narrow thermal decomposition of the PS-b-P4VP lead to nanopores in the prepared films from the results of TGA, AFM, and TEM. The effects of the loading ratio on the morphology and properties of the prepared nanoporous PMSSQ films were investigated. The TEM and AFM studies show that the uniform pore morphology with pore size 10-15 nm can be prepared from a modest porogen loading level for the optimum intermolecular hydrogen bonding. The refractive index and dielectric constant of the prepared nanoporous films decreases with an increase in PS-b-P4VP loading. On the other hand, the porosity increases with an increasing PS-b-P4VP loading. This study demonstrates a methodology to control pore morphology and properties of the nanoporous PMSSQ films through the templating of PS-b-P4VP.     

The preparation of nanoporous siloxane films using saccharide derivatives as new porogen

The porous siloxane thin film containing nanopores (<5.0 nm) can be effectively prepared by using an acyl mono/di-saccharide compound through porogen templated approach. The saccharide compound used as a porogen in this study effectively made pores in the siloxane thin film through their decomposition during hard curing process. The saccharide compounds seem to be assembled into adequate domain size in the silsesquioxane polymer via the intermolecular interaction between acyl groups of the porogens. The pore diameter of porous siloxane film prepared with 30 wt.% of benzoyl sucrose in spin-coating solution was 2.2 nm based on positronium annihilation lifetime spectroscopy. The saccharide derivatives templated nanoporous siloxane thin films showed the low dielectric property (k<2.5).     

Gas adsorption gates based on ultrathin composite polymer films

High surface area alumina coatings were prepared on surface acoustic wave (SAW) mass balances. These coatings were fabricated by anodic etching of evaporated aluminum films. The coatings consisted of roughly collinear pores penetrating through the monolithic alumina film. The nanoporous (NP) coatings were characterized by scanning electron microscopy, and the pore number density and diameter were found to be (3.8 +/- 0.5) x 10(3) pores/microm2 and 6.8 +/- 4.8 nm, respectively. The mass of volatile organic compounds that adsorbed onto naked and chemically modified NP alumina coatings was measured using SAW mass balances and compared to the mass absorbed onto SAW devices having planar aluminum coatings. Thirty-four times more heptane adsorbed to the naked NP coating than to the planar coating. The mass loading response was also measured after modification with organic thin films (3-12 nm thick) that spanned the pores of the NP coating. These organic thin films were composed of sixth-generation, amine-terminated poly(amido amine) dendrimers and poly(maleic anhydride)-c-poly(methyl vinyl ether) (Gantrez). The key result of this study is that these organic thin films modulate adsorption of VOCs onto the pore walls of the NP alumina. Specifically, a single 3-nm-thick monolayer of the dendrimer reduces permeability of the VOCs by approximately 17%, whereas a 12-nm-thick G6-NH2/Gantrez composite reduces permeability by 100%. Thus, the polymer composite acts as a nonselective gate that controls access of VOCs to the underlying surface area of the pores.     

Controlling pore morphology and properties of nanoporous silica films using the different architecture PS-b-P2VP as a template

Nanoporous silica films were prepared through the templating of amphiphilic block copolymer, poly(styrene-2-vinyl pyridine) (PS-b-P2VP), and monodispersed colloidal silica nanoparticles. The experimental and theoretical studies suggested that the intermolecular hydrogen bonding existes between the colloidal silica nanoparticles and PS-b-P2VP. The effects of the loading ratio and P2VP chain length on the morphology and properties of the prepared nanoporous silica films were investigated. TEM and AFM studies showed that the uniform pore size could be achieved and the pore size increased with increasing porogen loading. The refractive index and dielectric constant of the prepared nanoporous films decreased with an increase in PS-b-P2VP loading. On the other hand, the porosity increased with an increasing PS-b-P2VP loading. This study demonstrated a methodology to control pore morphology and properties of the nanoporous silica films through the templating of PS-b-P2VP.     

Mounted nanoporous anodic alumina thin films as planar optical waveguides

Solid-supported thin films of self-organized nanoporous anodic aluminum oxide (AAO) have been widely employed for the template preparation of nanostructured functional materials. Recently, the use of nanoporous AAO thin films in optical waveguide spectroscopy (OWS) has been explored for high sensitivity, in situ monitoring of processes occurring within these nanoporous templates. In this contribution, we demonstrate a strategy for mounting bulk anodized AAO thin films on heterogeneous solid-supports suitable for waveguide sensing experiments. Unlike conventional preparations of AAO thin films by anodization of vacuum- or electrochemically deposited Al thin films, the full range of techniques available to anodize bulk Al may potentially be applied with the present method. Moreover, we show that AAO thin films mounted on glass substrates can have superior waveguide coupling properties compared to conventionally prepared samples. The nanostructure of the AAO can be well characterized by an EMT-OWS analysis, demonstrated by comparing scanning electron microscopy images of the AAO and the pore dimensions calculated from an effective medium theory (EMT) analysis of the film refractive index measured by OWS. Finally, using a curved metallic substrate as an example, we show that our mounting technique can be used as a general strategy to functionalize objects with nanoporous AAO films.     

Solar-light photoamperometric and photocatalytic properties of quasi-transparent TiO2 nanoporous thin films

Transparent photocatalytic surfaces are of ever increasing importance for many applications on self-cleaning windows and tiles in everyday applications. Here, we report the formation and photocatalytic testing of a quasi-transparent thin and nanoporous titania films deposited on glass plates. Sputtered Ti thin films were anodized in fluoride-ion-containing neutral electrolytes to form optically semitransparent nanoporous films, which transformed to be completely transparent after thermal annealing. The nanoporous films were studied at different stages, such as before and after anodization, as well as after thermal annealing using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis and Raman spectroscopy. It was observed that anodization at 20 V of high-temperature deposited titanium films resulted in regular nanopore films with pore diameters of 30 nm. Structural investigations on the transparent nanopore arrays reveal the presence of anatase phase TiO(2) even after annealing at 500 °C, which was confirmed by XRD and Raman spectroscopy measurements. The solar-light induced photocatalytic decomposition of stearic acid and photoconductivity characteristics of these nanoporous thin films are also presented.     

Instabilities in nanoporous media

Rayleigh instabilities in thin polymer films confined within nanoporous alumina membranes were studied. Thin films of poly(methyl methacrylate) (PMMA) were prepared by filling cylindrical nanopores in an anodic aluminum oxide (AAO) membrane with a PMMA solution in chloroform followed by solvent evaporation. When the PMMA nanotubes were annealed above the glass transition temperature (Tg), undulations in the film thickness were observed that were induced by a Rayleigh instability. The amplitude of the undulations increased with time and eventually bridged across the cylindrical nanopore in the AAO membrane, resulting in the formation of polymer nanorods with periodic encapsulated holes. A similar behavior was observed when PMMA films were confined within carbon nanotubes (CNTs). The Rayleigh instabilities in these confined geometries offer a novel means of controlling and fabricating the polymer nanostructures. These compartmentalized nanorods may have potential applications as delivery devices.     

Quartz crystal microbalance and infrared reflection absorption spectroscopy characterization of bisphenol A absorption in the poly(acrylate) thin films

The absorption process of bisphenol A (BPA) in a number of poly(acrylate) thin films, such as poly(2-methoxyethyl acrylate) (PMEA), poly(ethyl acrylate) (PEA), poly(n-butyl methacrylate) (PBMA), and poly(methyl methacrylate) (PMMA), has been investigated by quartz crystal microbalance (QCM) and infrared reflection absorption spectroscopy (IRRAS) measurements. Both QCM and IRRAS measurements show that the BPA molecules absorb in PMEA, PEA, and PBMA thin films but not in PMMA thin film. The differences in the BPA absorption behavior are mainly attributed to the difference in the glass transition temperature (T(g)) between these polymers. This absorption behavior also depends on the BPA concentration and polymer film thickness. Furthermore, IRRAS characterization demonstrates that the hydrogen bonding is formed between the hydroxyl group in BPA and the carbonyl group in the poly(acrylate) thin films. BPA molecule absorbed in these polymer thin films can be removed by ethanol rinse treatment. By optimizing experimental conditions for the QCM electrode modified by PMEA thin film, detection limitation of approximately 1 ppb for BPA can be realized by the in situ QCM measurement. This method is expected to be a sensitive in situ detection way for trace BPA in the environmental study.     

Fusion of porous isotactic poly(methyl methacrylate) thin films fabricated on silica nanoparticles with stepwise stereocomplex assembly

Structures of silica nanoparticles coated with stereocomplex thin films composed of isotactic (it) poly(methyl methacrylate) (PMMA) and syndiotactic (st) poly(methacrylic acid) (PMAA) and with porous it-PMMA thin films under gentle stirring or static conditions were analyzed by dynamic light scattering (DLS) and scanning electron microscopy (SEM), respectively. The porous it-PMMA films were fabricated by stepwise stereocomplex assembling of it-PMMA and st-PMAA, and subsequent extraction of the st-PMAA from the films. From DLS results, an evident difference was not observed between the it-PMMA films and the stereocomplex films, whereas the it-PMMA films after 10 h of stirring in acetonitrile/water (4/6, v/v) and drying on a SEM stage fused to form nanostructured networks. The fusion of the it-PMMA films on the silica nanoparticles occurred not by the dissolution of it-PMMA in the mixed solvent, but rather by an interaction of the it-PMMA chains driven by the slight solvation of acetonitrile without dissolution. Thus, leaving the solution at rest would be important for film fusion on the particles, and multiple spherical substrates could promote the crosslinking of the it-PMMA chains on the particles.