非超临界干燥法制备SiO2气凝胶

应用廉价的国产硅溶胶为原料，通过凝胶过程和干燥过程条件的选择，以非超临界干燥技术最终获得了块状SiO2气凝胶.该气凝胶外观状态与应用正硅酸乙酯为原料制得的完全一致，其微观结构也相当良好，其直径和孔分布均匀.溶液的配比和pH对凝胶过程和气凝胶样品的密度有比较明显的影响，同时pH值与SiO2的粒径之间也有一定的关系.依据制备条件的变化，所得SiO2气凝胶的密度约在200～400 kg•m－3，比表面在250～300 m2•g－1之间变化，平均孔径约为11～20 nm，而孔隙率在91％左右.     

TiO2/SiO2气凝胶微球的制备及其表征

以TiOSO4和硅溶胶为原料, 加入甲酰胺作为干燥控制化学添加剂, 采用W/O乳状液中的溶胶-凝胶法制备TiO2/SiO2凝胶微球, 通过正硅酸乙酯母液浸泡、溶剂交换、陈化和常压干燥技术制备TiO2/SiO2气凝胶微球, 采用光学显微镜、SEM、TEM和BET比表面及孔分布测定等手段对所得样品进行表征. 典型的气凝胶微球样品是由粒径15 nm左右, 粒度分布相当均匀的球状纳米粒子构成的轻质纳米多孔材料, 表观密度为177 kg•m-3, 比表面积372 m2•g-1, 平均孔径22.78 nm, 孔隙率高达92.0％, 微球的宏观粒径为50 m. 依据制备条件的变化, TiO2/SiO2气凝胶微球的宏观粒径可控在10～200 m之间, 表观密度为150～300 kg•m-3, 比表面积为300～400 m2•g-1, 平均孔径在18.71～22.78 nm之间变化.     

块状TiO2/SiO2气凝胶的非超临界干燥法制备及其表征

分别通过TiO2和SiO2的单独溶胶和TiO2/SiO2复合凝胶,并添加干燥控制化学添加剂甲酰胺,形成比较完善的凝胶网络结构,同时通过正硅酸乙酯的乙醇溶液浸泡,低表面张力溶剂替换和分级陈化以及干燥等步骤,实现了块状TiO2/SiO2复合气凝胶的非超临界干燥制备.所得TiO2/SiO2气凝胶为无色或乳白色轻质块状多孔固体,表观密度约0.4～0.9g/cm3,孔隙率约80%～95%.它由直径约10nm的TiO2和SiO2微粒相互分散复合而成,孔洞直径约几十纳米.其相态SiO2为无定形,TiO2为锐钛矿晶型.随着焙烧温度的升高,直到800℃不发生相变化.     

超临界干燥法制备Fe2O3-SiO2气凝胶

以正硅酸乙酯（TEOS）和硝酸铁为原料,采用溶胶-凝胶法和超临界干燥工艺制备了Fe2O3-SiO2气凝胶,研究了Fe2O3-SiO2醇凝胶的形成条件的影响,并对所得气凝胶样品结构特性进行了初步表征．所得气凝胶样品是由直径约8nm的胶体粒子构成的低密度、高孔隙率的块状非晶固态材料．     

三甲基氯硅烷对纳米多孔二氧化硅薄膜的修饰

以正硅酸乙酯为先驱体,采用溶胶-凝胶法,结合旋转涂胶、超临界干燥工艺在硅片上制备了纳米多孔SiO2薄膜.用三甲基氯硅烷(TMCS)对该SiO2薄膜进行了表面修饰,采用FTIR、TG-DTA、AFM和椭偏仪等方法研究了TMCS修饰前后薄膜的结构、形貌、厚度与介电常数等性能.超临界干燥后的SiO2薄膜含有Si－O－Si与Si－OR结构,呈疏水性.在空气中250 ℃以上热处理后SiO2薄膜因含有Si－OH而呈吸水性. TMCS修饰后的SiO2薄膜在温度不高于450 ℃时可保持其疏水性和多孔结构. SiO2薄膜经TMCS修饰后基本粒子和孔隙尺寸增大,孔隙率提高,介电常数可降低至2.5以下.     

原位法常压干燥制备疏水SiO2气凝胶及其热稳定性

在正硅酸乙酯(TEOS)酸碱两步催化的溶胶-凝胶过程中, 加入干燥控制化学添加剂(DCCA)N,N-二甲基甲酰胺(DMF)和三甲基氯硅烷(TMCS)的混合溶液, 进行原位疏水改性处理, 并结合常压干燥工艺制备了高比表面积的疏水SiO2气凝胶. 利用N2物理吸附, 全自动X射线衍射仪(XRD), 傅立叶变换红外光谱仪(FTIR), 扫描电子显微镜(SEM)等对样品的形貌结构进行了表征. 实验结果表明, 原位疏水改性比非原位疏水改性制备的SiO2气凝胶具有更大的比表面积, 可达979 m2·g-1, 气凝胶表面存在憎水性基团—CH3, 有良好的疏水性. 500 ℃热处理后, 气凝胶因失去大量的—CH3基团, 由憎水性转为亲水性; 800 ℃高温热处理后, 疏水SiO2气凝胶仍处于非晶态, 具有良好的热稳定性能.     

NiO/SiO2气凝胶催化剂性能研究 Ⅰ. 镍含量的影响

以硝酸镍和正硅酸乙酯为原料采用溶胶凝胶超临界流体干燥法制备了不同镍含量的气凝胶催化剂.XRD,TPR,TEM,IR等物理技术表征和顺酐液相催化加氢活性评价结果表明NiO/SiO2气凝胶催化剂中NiO与SiO2有较强的相互作用,镍含量对活性组分与载体之间相互作用的影响导致催化剂具有不同的丁二酸酐和γ-丁内酯的选择性.在镍含量为30w%,经673K焙烧的催化剂上γ-丁内酯的选择性最佳.     

新的溶胶-凝胶法制备Ge/SiO2量子点玻璃

以3－三氯锗丙酸和正硅酸乙酯为原料,通过水解、缩聚凝胶热处理及氢气反应,在SiO2凝胶玻璃中析出立方相Ge纳米晶,当x=30时,凝胶玻璃中除了析出立方相Ge纳米晶处,还析出六方相GeO2,利用XRD测试了Ge纳米晶的大小,发现随着掺杂量的增加,纳米颗粒粒径从1nm增大到10nm,电子衍射表明镶嵌在SiO2凝交玻璃中的Ge纳米晶为多晶结构。     

溶胶-凝胶法制备镶嵌在SiO_2玻璃中的InAs纳米晶

以As2 O3,InCl3·4H2 O和正硅酸乙酯为原料 ,通过水解、缩聚制备了xIn2 O3-xAs2 O3- 10 0SiO2 (x =0 .5～ 7.5 )凝胶 .在氧气中加热到 45 0℃对凝胶热处理使其转化成凝胶玻璃 ,再在 2 0 0～ 5 0 0℃与氢气反应 ,结果在SiO2 凝胶玻璃中形成了立方相InAs.利用XRD测试了InAs纳米颗粒的大小 ,发现随着反应温度的升高及掺杂量的增加 ,InAs纳米颗粒粒径从 6增大到 2 9nm .电子衍射表明凝胶玻璃中的InAs纳米颗粒为多晶结构     

纳米孔莫来石陶瓷材料的制备

以正硅酸乙酯(TEOS)提供硅源、纳米氧化铝(d90=50 nm)提供铝源,通过溶胶-凝胶法与超临界干燥技术,制备了分散纳米氧化铝的SiO2气凝胶块体,所得复合气凝胶块体经1200℃、1300℃热处理后,得到了纳米孔莫来石陶瓷材料。XRD测试表明:凝胶体在1 200℃热处理后发生了莫来石化,1300℃莫来石化基本完成。压汞仪与场发射扫描电镜结果显示:凝胶块体经1 200、1 300℃热处理后,形成了具有纳米多孔结构的莫来石陶瓷材料,其骨架结构包含有200~400 nm的大孔,以及大量位于其孔壁上的6~30 nm的介孔。由于莫来石化的进行,热处理后的陶瓷材料的纳米孔结构具有更高的热稳定性。     

Synthesis of freestanding silica and titania-silica aerogels with ordered and disordered mesopores

Freestanding blocks of silica and titania-silica aerogels were prepared by the sol-gel method. It is possible to prepare crack-free, titania-silica aerogels with high titanium content by a careful control of the synthesis conditions. Prehydrolysis, complexation and polymer addition were used to adjust the hydrolysis and condensation rates of the silicon and titanium alkoxide precursors. Photoactive anatase TiO₂ nanocrystals with a large surface area (i.e., up to 300m²g⁻¹) were crystallized from the gel network by the high-temperature ethanol supercritical drying, and the resulting aerogel blocks were gas permeable and display a transition-regime diffusion behavior. Pore and volume shrinkages were observed in samples prepared by ethanol supercritical drying when the titanium content was increased resulting in a lower flux. Adding Pluronic P123 creates ordered mesopore domains and produces large pore aerogels even at high titanium contents. The photocatalytic oxidation reaction of trichloroethylene was performed by flowing the reactant gas mixture through the UV-irradiated aerogel blocks with excellent results.     

Ambient pressure dried tetrapropoxysilane-based silica aerogels with high specific surface area

In the present paper, we report the synthesis of tetrapropoxysilane (TPOS)-based silica aerogels with high surface area and large pore volume. The silica aerogels were prepared by a two-step sol-gel process followed by surface modification via a simple ambient pressure drying approach. In order to minimize drying shrinkage and obtain hydrophobic aerogels, the surface of the alcogels was modified using trichloromethylsilane as a silylating agent. The effect of the sol-gel compositional parameters on the polymerization of aerogels prepared by TPOS, one of the precursors belonging to the Si(OR)₄ family, was reported for the first time. The oxalic acid and NH₄OH concentrations were adjusted to achieve good-quality aerogels with high surface area, low density, and high transparency. Controlling the hydrolysis and condensation reactions of the TPOS precursor turned out to be the most important factor to determine the pore characteristics of the aerogel. Highly transparent aerogels with high specific surface area (938 m²/g) and low density (0.047 g/cm³) could be obtained using an optimized TPOS/MeOH molar ratio with appropriate concentrations of oxalic acid and NH₄OH.     

气相扩散速率对溶菌酶晶体生长的影响

为研究气相扩散速率对溶菌酶晶体生长的影响,特设计了一种可方便调节气相扩散速率的晶体生长样品池,并用动态光散射法对不同气相扩散速率下晶体生长过程进行了研究.实验结果表明,随着气相扩散速率的增加,晶体生长过程中的成核阶段缩短.气相扩散速率通过影响溶菌酶溶液形成过饱和的速率来影响生长出的晶体的数量和大小.     

溶胶－凝胶法制备超细SiO_2──制备参数对气凝胶织构性质的影响

ＳｉＯ_２气凝胶超细粉由ＴＥＯＳ（正硅酸乙酯）在乙醇溶液中水解聚合后经超临界流体干燥（ＳＣＦＤ）制得。本文考察了ＴＥＯＳ的浓度、水和ＴＥＯＳ的摩尔比以及焙烧温度对超细粉织构性能的影响。结果表明，超细ＳｉＯ_２的比表面积、总孔容、孔分布、最可几孔径及表现堆密度均随制备参数而改变。而以ＳｉＯ_２气凝胶超细粉体为基本载体材料的Ｃｏ／ＺｒＯ_２－ＳｉＯ_２催化剂显示出高的ＣＯ＋Ｈ_２合成重质烃的活性和选择性。     

Organofunctional Silica Aerogels

Organically modified silica aerogels were prepared from mixtures of tetramethoxysilane (TMOS) and organofunctional alkoxysilanes RSi(OMe)₃ with R=mercaptopropyl, diphenylphosphinoethyl and chloropropyl. The base catalyzed hydrolysis and condensation reactions, followed by supercritical drying with liquid carbon dioxide were investigated. Starting from 9:1 mixtures of TMOS and RSi(OMe)₃, incorporation of the functional moieties succeeded quantitatively. Increasing the percentage of RSi(OMe)₃ to 20% or 40% leads to an incomplete condensation of the RSiO_1,5 units to the SiO₂ network. Compared with an unmodified silica aerogel, the microstructure of the resulting hybrid aerogels is nearly uninfluenced for the 9:1 mercapto-and chloro-modified samples, while in the phosphino-modified sample the typical pore radii distribution is disturbed by the bulky organic groups. The organofunctional aerogels decompose between 210 and 650°C.     

Physical Properties of Silica Aerogels Prepared with Polyethoxydisiloxanes

Silica aerogels were made by sol-gel techniques using industrial silicon derivatives (polyethoxydisiloxanes, E-40), followed by supercritical drying with ethanol. The morphology and microstructure of the silica aerogels were investigated by using specific surface area, S_BET, SEM, TEM and the pore size distribution techniques. The thermal conductivity was also measured as a function of air pressure. The results show that the diameter of the silica particles is about 13 nm and the pore size of the silica aerogels is 20–80 nm. The specific surface area of the silica aerogel is about 470 m²/g and the thermal conductivity of the silica aerogel prepared with E-40 is 0.014 w m^–1 K^–1 at room temperature and 1 atm.     

Large Scale Porous Structure in Gels and Relationship with Their Plastic Behavior

Silica gels (classical aerogels and composite aerogels) have been prepared by classical gelation and addition of silica soot in the gelifying solution before gelation. Due to the aggregation mechanisms, these structures are characterized by a fractal organization. The fractal network previously described in the literature (1–100 nm) which results from the aggregation mechanism of the organosiloxane is affected by the addition of the silica soots. Ultra Small Angle X-ray Scattering (USAXS) experiments (done at ESRF) shows that besides the fractal network built by the organosiloxane, the silica soots are forming another porous structure at a higher scale.The mechanical properties seem to be dependent on this large pore structure. Under isostatic pressure, aerogels display an irreversible shrinkage caused by plastic deformation. As a consequence of this plastic shrinkage it is possible to densify, by the pore collapse tending towards the silica glass. The densification mechanism is different from the one obtained by a sintering at high temperature. The pore collapse mechanism is favored by the large pores structure of the composite aerogels, in contrast to viscous sintering.