小角x射线散射法研究甲基改性氧化硅凝胶的双分形结构

以正硅酸乙酯［Si(OC2H5)4,TEOS］和甲基三乙氧基硅烷［CH3Si(OC2H5)3,MTES］为前驱体，通过共水解法和两步法制备出两种不同的甲基改性氧化硅凝胶，在北京同步辐射光源(BSRF)小角x射线散射(SAXS)站测量了凝胶的散射强度，计算了凝胶的平均粒径、两相间比表面积等参数，在此基础上分析了凝胶的分形特征，发现存在两个尺度上的分形结构，分别对应于从SiO2原生颗粒到一次团聚体和从一次团聚体到簇团两种尺度.辅以透射电子显微镜(TEM)观测，证实由两种方法获得的凝胶具有非常不同的微观结构.实验证明，利用SAXS技术研究甲基改性凝胶的分形特征是获得凝胶微观结构的有力工具. 关键词： 甲基改性凝胶 氧化硅 小角x射线散射(SAXS) 分形结构     

表面修饰纳米碳管复合二氧化硅凝胶玻璃的制备研究

采用羧基化、酰氯化和酰胺化等三步化学反应实现了r-氨基丙基三乙氧基硅烷(NH2(CH2)3Si(OC2H5)3,APTES)对纳米碳管(CNTs)的表面修饰.在此基础上,采用溶胶-凝胶工艺将其引入到二氧化硅凝胶玻璃中,并通过红外IR光谱、扫描电子显微镜SEM分析测试方法对所得样品的组成和结构进行表征.结果表明,经过一系列的化学处理,成功实现了CNTs与APTES的共价键合而达到表面修饰的效果.溶胶一凝胶过程中,先驱液中正硅酸乙酯(Si(OC2H5)4,TEOS、r-缩水甘油醚基丙基三甲氧基硅烷(CH2OCH2O(CH2)3Si(OCH3)3,GPTMS)、CNTs-APTES分别发生水解,并经过共同聚合反应形成二氧化硅三维网络结构,而CNTs也借助于APTES而被化学键合到二氧化硅网络中,实现了在二氧化硅凝胶玻璃基质中的均匀分散,从根本上克服了CNTs在固相基质中团聚的问题.     

Ni2（OCH3）2／SiO2催化剂上C02和CH30H的吸附和反应性能

采用表面改性和离子交换相结合的方法制备了Ni2(OCH3)2／Si02负载型双核金属甲氧基配合物催化剂，利用红外光谱(IR)、程序升温脱附(TPD)、程序升温表面反应(TPSR)和微反技术考察了催化剂的表面结构以及C02和CH30H的化学吸附和反应性能．结果表明：Ni2(OCH3)2／SiO2中Ni^2+与载体SiO2表面O^2-以双齿配位形式键合，甲氧基以桥基形式联结双金属离子形成双核物种Ni2(OCH3)2；CO2在催化剂表面存在甲氧碳酸酚基物种和桥式两种吸附态，CH30H则只有一种分子吸附态；在100—200℃条件下，C02和CH30H在催化剂上的反应产物主要是DMC和H20；根据反应结果，讨论了催化反应机理．     

三维有序大孔聚苯乙烯的制备及表征

采用播种生长法制备了粒径为330 nm的单分散胶体二氧化硅（SiO2），并对单分散的SiO2颗粒表面进行改性，以提高颗粒对苯乙烯单体的亲和力.然后通过垂直沉积法组装出SiO2胶粒晶体模板.依靠毛细管力将苯乙烯前驱物快速填充进模板颗粒的间隙，加热原位聚合 ，用氢氟酸去除模板后制得三维有序大孔聚苯乙烯.扫描电子显微镜结果显示，所合成的孔材料高度有序，孔腔尺寸约为210 nm，孔腔之间由较小孔窗连接，形成非常开放的通道网络 . 关键词： 三维有序大孔材料(3DOM) 聚苯乙烯 模板 二氧化硅     

多面体低聚倍半硅氧烷-ZrO2复合气凝胶的制备与表征

以官能团化的多面体低聚倍半硅氧烷（POSS-［C2H4Si(OEt)3］8）和正丁醇锆为原料,以乙醇作为溶剂,通过溶胶-凝胶及二氧化碳超临界干燥成功制备了三种不同锆含量POSS-ZrO2的复合气凝胶。并用傅里叶变换红外光谱分析仪（FTIR）、扫描电镜（SEM）、X射线衍射仪（XRD）和比表面吸附仪（BET）对其进行表征。结果表明:该气凝胶中有SiOZr键,并且所得气凝胶都是无定型的,其比表面积随着锆含量的增加而变小,最高可达491 m2/g,并且其孔径分布都比较广。     

甲基对钌配合物与DNA相互作用的瞬态发光特性的影响

采用时间分辩的发光光谱技术,测量了新合成的钌配合物［Ru(phen)2(7 CH3 dppz)］2+与小牛胸腺DNA相互作用的瞬态发光动力学过程,并与以往研究的配合物［Ru(phen)2(dppz)］2+和［Ru(phen)2(dppx)］2+的瞬态发光特性进行对比,更全面地研究了甲基对钌配合物与DNA相互作用的瞬态发光特性的影响.［Ru(phen)2(7 CH3 dppz)］2+的结构介于［Ru(phen)2(dppz)］2+和［Ru(phen)2(dppx)］2+之间,但发光寿命却比这两种配合物短,表明了甲基的疏水性、空间位阻及推电子能力对配合物的发光寿命均有影响.该结论为进一步研究配合物分子与DNA的相互作用的机理提供了一定的依据.     

高择优取向硅基含钾铌酸锶钡（K:SBN）薄膜的制备与性能

采用NbCl5作为先驱物，利用溶胶-凝胶法在Si(100)衬底上成功获得高度择优取向的铁电铌酸锶钡(SBN)薄膜.与用Nb(OC2H5)5作为先驱物的SBN薄膜相比，NbCl5配制的薄膜前驱溶液中含有一定数量的K离子.K离子的含量对SBN薄膜取向的影响存在一个最优值.二次离子质谱测试发现，K离子对SBN晶胞的溶入和对Si衬底的渗透能够同时使SBN晶胞和Si晶胞产生微小扭曲，从而起到调整薄膜与衬底的匹配关系，并最终促使SBN薄膜c轴高度择优取向的生长.测试了薄膜的光学特性. 关键词： 铌酸锶钡 溶胶-凝胶方法 择优取向     

磷酸盐激光玻璃聚(CH3)2 Si(OC2 H5)2防潮膜

以（CH3）2Si（OC2H5）2为前驱体，采用溶胶-凝胶与有机合成相结合的方法，制得稳定性良好的涂膜液。采用旋转涂膜法在掺钕磷酸盐激光玻璃棒端面涂制防潮膜，膜层固化后透过率达96．5％，获得的膜层表面粗糙度优良，均方根表面粗糙度（RMS）为1．659nm，平均粗糙度（RA）平均为1．321nm；在激光波长1053nm，脉冲宽度1 ns条件下膜层的激光破坏闽值可达10～14 J／cm^2。经过“神光Ⅱ”高功率激光器物理实验运行，膜层使用期为五年，并且已经在我国“神光Ⅲ”原型装置上试用。     

Mesoporous Silica Materials Synthesized via Sol-Gel Methods Modified with Ionic Liquid and Surfactant Molecules

采用离子液体1-甲基-3-丁基咪唑四氟硼酸盐改性的溶胶-凝胶法以及表面活性剂十六烷基三甲基溴化铵进一步改性的溶胶-凝胶法制备介孔二氧化硅. 通过X射线衍射、氮气吸附脱附和扫描电子显微镜对所制备的样品进行表征. 结果表明，与仅用离子液体为模板制备的介孔二氧化硅相比，采用表面活性剂和离子液体的混合物为模板制备的介孔二氧化硅具有较小的孔径和较规则的孔结构. 说明利用该方法制备介孔二氧化硅，表面活性剂的加入会在一定程度上影响所制介孔二氧化硅的微结构.     

单甲基原位改性SiO2疏水减反膜的制备与性能研究

 在碱性条件下通过TEOS和MTES的共水解缩聚反应制备了单甲基原位改性的SiO₂溶胶，并使用提拉法在K9玻璃基片上镀制了疏水减反膜。通过透射电镜（TEM）考察了镀膜溶胶的微结构，分别使用红外光谱（FTIR）分析了薄膜的组分，用原子力显微镜（AFM）观察了薄膜的表面形貌和起伏状况，用紫外可见光谱（UV-vis）考察了薄膜的减反射性能，用接触角仪测量了薄膜对水的接触角。并使用“R-on-1”的方式测量了薄膜在Nd:YAG激光（1 064 nm，1 ns）作用下的损伤阈值。结果表明，通过共水解缩聚反应可以把甲基引入镀膜溶胶簇团中，改善了溶胶簇团的网络结构，使薄膜得到相当好的疏水性能和更好的抗激光损伤性能，同时薄膜能保持较好的减反射性能。     

小角X射线散射方法测定二氧化硅干凝胶的平均孔径

提出了当多孔体系的小角X射线散射不遵守Porod定理的情况下,应用Debye法(相关函数法) 和Guinier法(逐级切线法和多级斜线法)计算它们的平均孔径的方法.对不同制备条件下部分 二氧化硅干凝胶的测试,取得了比较一致的结果,并与氮气吸附法测定结果进行了对比. 关键词： 小角X射线散射 二氧化硅干凝胶 平均孔径     

Adsorption characterization of surfactant-templated ordered mesoporous silicas synthesized with and without hydrothermal treatment

This work reports a systematic study of ordered mesoporous silicas (OMSs) synthesized with and without hydrothermal treatment at 373 K for a series of surfactants of different alkyl chain length (from C10 to C18). For these samples nitrogen adsorption and small angle X-ray scattering (SAXS) data were measured to characterize their adsorption and surface properties. Namely, nitrogen adsorption isotherms were used to evaluate their specific surface area, pore volume and pore size distribution, whereas SAXS data provided information about their structural ordering. It is shown that while the room temperature synthesis afforded OMS samples with cubic MCM-48 structure, an additional 5-day hydrothermal treatment of these samples at 373 K caused their transformation to MCM-41 (two-dimensional hexagonal structure) and improved their pore uniformity, which was manifested by reducing the width of pore size distribution.     

气体吸附法测定二氧化硅干凝胶的分形维数

提出了一种方便、科学有效的利用气体吸附法测定二氧化硅干凝胶等多孔材料分形维数（表面分形维数和孔分布分形维数）的方法，不需要进行一系列的吸附/脱附实验，只需要利用单一气体的一次吸附/脱附实验得出的样品孔分布、比表面数据，与不同的标尺进行关联，即可同时获得表面分形维数和孔分布分形维数.通过误差分析和校正，保证了结果的可靠性.用上述方法测定了二氧化硅干凝胶的分形维数，以FHH法和SAXS法对所得结果进行了比较和验证，并对吸附/脱附过程所得结果的差异进行了初步分析. 关键词： 分形维数 气体吸附 二氧化硅 干凝胶     

Methyl orange adsorption by microporous and mesoporous TiO2-SiO2 and TiO2-SiO2-Al2O3 composite xerogels

We investigate the adsorption behavior of methyl orange (MO) on composite xerogels. Mesoporous TiO₂-SiO₂ and TiO₂-SiO₂-Al₂O₃ xerogels are prepared by hydrolysis of tetraethyl orthosilicate (TEOS), tetrabutyl orthotitanate (TBOT), and AlCl₃ ·6H₂O using HCl as a catalyst and cetyltrimethylammonium bromide (CTAB) as a templating agent. The corresponding microporous xerogels are also prepared without addition of CTAB. These xerogels are then characterized by XRD, FTIR, and BET.We find that MO is adsorbed by the mesoporous xerogels in acidic solutions, showing Langmuir type adsorption isotherms. We also find that the adsorption decreases with increasing temperature. It is suggested that adsorption exhibits a sieve effect and that MO is adsorbed through electrostatic attraction and hydrogen bonding between MO and the xerogels.     

Design of organic supercapacitors with high performances using pore size controlled active materials

In this study, we thoroughly investigate the required properties of active materials for organic supercapacitors with high performances. In this regard, we synthesize carbon xerogels with different physical properties, including specific surface area and pore size. The carbon xerogels are prepared via the sol-gel reaction of resorcinol and formaldehyde under different gelation temperature conditions. Through Fourier-transform infrared, nitrogen adsorption–desorption, and scanning electron microscopy analysis, we can confirm that carbon xerogels with different physical properties can be successfully synthesized. We apply the prepared carbon xerogels to organic supercapacitor electrodes. As a result of electrochemical experiments, carbon xerogels with high surface area exhibit high electrochemical performances at low-rate charge?discharge processes. However, as the charge–discharge rate increases, carbon xerogels with low surface area and high conductivity exhibit higher performances. Therefore, the surface area of active materials is a key factor for supercapacitors with high performances at low-rate charge–discharge processes. However, the effects of conductivity can be more crucial as compared with those of surface area as the charge–discharge rates increase. In addition, we suggest that the physical properties of active materials should be differently optimized as the charge–discharge rate is employed.     

Eu掺杂SiO2纳米基质的发光特性

采用溶胶-凝胶(sol-gel)法制备了Eu掺杂的SiO₂干凝胶,分别用光致发光(PL)光谱、透射电镜(TEM)、扫描电镜(SEM)、红外吸收(IR)谱等分析手段对样品进行了表征,研究了SiO₂的基质中Eu³⁺、Eu²⁺的发光特性以及退火温度对发射光谱的影响,并对其发光机理进行了分析。结果表明,样品掺杂均匀,颗粒尺寸大约在50~80 nm,硼(B)离子进入SiO₂网格,成为了基质的一部分,改变了基质的网络结构。当采用258 nm激发样品时,随着退火温度的升高,红光发射强度先增强后减弱。对于经800 ℃退火处理的样品红光发射最强,出现了576 nm(⁵D₀ →⁷F₀),620 nm(⁵D₀ →⁷F₂),658 nm(⁵D₀ →⁷F₃)3条谱线,其中主峰位于 620 nm红光发射,对应于Eu³⁺离子的⁵D₀ →⁷F₂超灵敏跃迁,进一步说明B离子参与到基质中,形成了Si—O—B键,导致Eu³⁺离子所处配位环境的对称性降低,从而有利于Eu³⁺离子的特征发射;当采用271 nm激发样品时,随着退火温度的升高,蓝光发射强度先增强后减弱,经850 ℃退火的样品400~500 nm蓝光发射最强,归属于Eu²⁺的5d→4f的跃迁发射,证明在铝离子(Al³⁺)存在的情形下,在高温退火过程中Al³⁺部分取代Si⁴⁺形成AlO^-₄基团,掺杂Eu³⁺填补AlO^-₄基团附近的空位,增加了Eu³⁺周围的AlO^-₄四面体中氧原子的电子给予能力,使得Eu³⁺还原成Eu²⁺,从而得到了较强的蓝光发射。但是,当退火温度达到900 ℃时,由于稀土离子发生位置的迁移形成团簇红光和蓝光都明显地降低。     

Vacuum Calcination Behavior of SBA-15 Ordered Mesoporous Silica

In this paper, the calcination of SBA-15 in vacuum is followed by in situ and ex situ small angle X-ray scattering (SAXS) measurements at different temperatures and the material properties are compared with the conventional calcination process in nitrogen and air. The whole process of template decomposition and by-products elimination is investigated as a function of temperature, showing early stages of polymer decomposition at 200 °C. The textural properties of the vacuum-calcined material, analyzed by nitrogen adsorption isotherm data at the end of the calcination process at 540 °C, revealed a smaller surface area and no detectable volume of micropores. A sharp monomodal pore size distribution with a mean value around 108 Å is obtained, larger than the material calcined via the usual procedure, which gives values around 98 Å. The results indicate that the vacuum heat treatment is an alternative calcination strategy for applications which require a well-ordered mesoporous structure, rigid pore walls, and large pore diameters.     

X-ray metrology for advanced silicon processes

X-ray reflectivity (XRR), X-ray fluorescence (XRF) and small angle X-ray scattering (SAXS) techniques are used to the monitoring of Cu/porous low κ processes, which are developed for the next generation (≤65 nm) integrated circuits. Sensitivity of XRR and XRF is sufficient to detect drifts of the copper barrier layer, copper seed layer and Cu CMP (chemical-mechanical polishing) processes. Their metrology key parameters comply with production requirements. SAXS allows determining the pore structure of low κ films: average pore size and pore size distribution.     

Porosity of microporous zeolites A, X and ZSM-5 studied by small angle X-ray scattering and nitrogen adsorption

Small-angle X-ray scattering (SAXS) using synchrotron radiation and nitrogen adsorption have been applied to characterizations of porosities and microporous structures for the zeolites of NaA, KA, CaA, NaX and ZSM-5. Besides the information on the external morphology of the particles of the zeolites, the complementation of the two techniques has revealed rich and consistent structural and surface information on the molecular scale crystalline pores of these zeolites. Analyses of the data suggest that the determined sizes of the micropores imply the pore spaces occupied by the probe molecules of water in the SAXS and nitrogen in adsorption techniques, respectively. The microporous information of NaA and KA are difficult to obtain from nitrogen adsorption, due to the blocking of nitrogen by their narrow channels, but have been satisfactorily measured by SAXS. The factors causing variations of the measured values of the parameters in different analysis methods have been discussed.