利用改进的本体溶胶-凝胶过程制备单组分二氧化硅单块

溶胶 -凝胶方法具有较低的反应温度 ,可在材料处理的最初阶段即纳米尺度上对材料的结构进行控制 ,所制备材料具有较高均一性和高纯度等优点 ,长期以来引起了众多科学家的关注[1～ 4 ] .然而 ,传统的溶胶 -凝胶工艺存在凝胶时间过长、体积收缩大、形状和尺寸无法控制、严重的龟裂、成本高以及环境污染等缺点 ,限制了其应用 .针对上述问题 ,我们改进了传统的溶胶 -凝胶过程 ,提出本体溶胶 -凝胶技术和复合本体溶胶 -凝胶技术 [1,2 ] .本体溶胶 -凝胶技术由于加入的凝胶促进剂碳酸盐与 Si O2 相容性差 ,存在块体成功率相对较低、表面不光滑和…     

一种有机酰腙类配体及其金属凝胶的结构及性能

设计合成了一种带有长链烷基和配位基团的新型有机配体2-吡啶甲醛-4'-十二烷氧基苯甲酰腙(简称L),并采用核磁(1H-NMR)、红外(FTIR)、电喷雾质谱(ESI-MS)和元素分析确认其结构.在乙醇和水的混合溶剂中,配体L可使溶剂凝胶化,并可与多种金属离子(Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ)和Cu(Ⅱ)作用,形成金属凝胶.采用扫描电镜分析表明,L自身形成的凝胶及金属凝胶的微观形貌均为相互搭接的纤维状结构.采用紫外光谱分析表明在乙醇溶液中L分子形成了聚集体.采用平板流变仪分析表明引入金属离子可提高凝胶的强度.进一步合成了L与Cu(Ⅱ)的配合物,通过对比配合物与金属凝胶的红外光谱和紫外光谱,证明金属凝胶中配体L与金属离子间形成了配位作用.     

一种氧化海藻酸钠基温敏凝胶的制备与性能

合成出一种具有温敏特性的多官能团的大分子聚(N-异丙基丙烯酰胺-丙烯酸甲酯-丙烯酰肼)(PNMH),用它交联氧化的海藻酸钠(OSA),得到可生物降解的温敏凝胶PNMH-OSA.分别以凝胶的透光率随温度变化和凝胶在磷酸盐缓冲液(PBS)中的溶胀比随时间变化来考察凝胶的温敏性能和降解性能,并采用傅立叶变换红外光谱(FTIR)和激光共焦拉曼光谱(LCRS)对样品进行了表征.结果表明,PNMH-OSA凝胶是通过PNMH上的—NHNH2和OSA上的—CHO反应生成C N键而形成的化学交联凝胶;随着凝胶中PNMH量的增加,PNMH-OSA凝胶的温敏性增强,降解时间延长;温敏组分的含量对PNMH-OSA凝胶的溶胀和降解性能与温度的关系影响显著.     

一种高强度准聚轮烷水凝胶的制备及性能研究

通过点击化学在聚乙二醇单甲醚(MPEG)端基分别修饰了葡萄糖(Glc)、甘露糖(Man)和半乳糖(Gal),制备了一系列端基为糖的聚乙二醇单甲醚(MPEG-Glc、MPEG-Man和MPEG-Gal),此类端基为糖的MPEG和α-环糊精(α-CD)混合后能够形成稳定的准聚轮烷(PPR)水凝胶,而端基没有修饰糖的MPEG和α-CD只能形成黏度较大的溶液而无法形成稳定存在的凝胶.通过流变仪测试可知水凝胶的弹性模量高达1.0×105 Pa,远大于文献中通过黏土等增强的PPR水凝胶的强度,我们认为该MPEG端基的糖之间能够形成新的"糖交联"点从而有效提高了凝胶的强度.通过向水凝胶中加入和MPEG端基的糖具有相互作用的苯硼酸半酯聚合物(PNIPAM-co-PBOB)或刀豆蛋白(Con A),发现在凝胶中加入PNIPAM-co-PBOB或Con A后可明显降低PPR水凝胶的强度.通过扫描电镜(SEM)和X射线衍射(XRD)对水凝胶的形貌以及微观结构进行表征分析,发现此凝胶的微观结构和文献中报道的PPR水凝胶基本一致,进一步证明了上述结论.     

采用大分子单体稳定印迹牛血清白蛋白

以牛血清白蛋白为模板蛋白质,聚(丙烯酸羟乙酯-乙烯基咪唑-1-(烯丙基乙酯)-3-乙烯基咪唑氯)[P(HEA-co-VIM-co-[AVIM]Cl)]为大分子功能单体和交联剂,通过氧化还原引发聚合法制备了蛋白质印迹水凝胶.圆二色光谱和同步荧光光谱结果表明,P(HEA-co-VIM-co-[AVIM]Cl)能够较好地维持牛血清白蛋白结构稳定性,而相同质量的HEA,VIM和氯化1-(烯丙基乙酯)-3-乙烯基咪唑([AVIM]Cl)的混合物对牛血清白蛋白的结构破坏严重.选择性吸附和竞争吸附的结果表明,用P(HEA-co-VIM-co-[AVIM]Cl)制备的印迹水凝胶比用HEA,VIM和[AVIM]Cl制备的印迹水凝胶具有更强的选择性和识别能力.在制备过程中维持模板蛋白质结构的稳定性有利于得到具有高识别能力和选择性的印迹聚合物.采用大分子单体印迹蛋白质的方法,可以有效地克服蛋白质在印迹过程中的结构容易变性的缺点,对蛋白质印迹技术的发展具有重要意义.     

聚富马酸丙二醇酯/羟基磷灰石复合多孔水凝胶的制备及其矿化性能研究

采用二步法合成了可降解的聚富马酸丙二醇酯(poly(propylene fumarate),PPF),并和N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)共聚,以1,4-二氧六环为溶剂,通过改变溶剂的量制备了溶胀性能不同的PPF水凝胶.采用万能力学测试仪和扫描电子显微镜分别表征了水凝胶的压缩模量和形貌结构.选择20％ PPF和10％ NVP的聚合体系,预掺3％的纳米羟基磷灰石(hydroxyapatite,HA),以氯化钠粒子为致孔剂,制备了孔径在280～450 μm的纳米复合多孔水凝胶,使其压缩模量提高了61％.模拟体液矿化10天的结果显示,磷灰石成核位点的存在和良好的与外界液体环境物质交换的能力,促进了多孔水凝胶表面磷灰石的沉积,说明HA的复合可以有效提高PPF多孔水凝胶的成骨活性.     

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.     

聚丙烯酸钠和丝素蛋白自膨胀水凝胶的制备及其释药性能

通过自由基聚合的方法合成制备了自膨胀PAAS-SF semi-IPN水凝胶(聚丙烯酸钠-丝素半互穿网络水凝胶),并进一步探讨其作为微创治疗中组织植入物的潜能.主要研究了SF(丝素蛋白)和AA(丙烯酸)的重量比对PAAS-SFsemi-IPN水凝胶的结构、膨胀性以及力学性能的影响.此外,我们还研究了抗生素药物阿莫西林(AMO)在PAAS-SFsemi-IPN水凝胶中的包载与释放性能.结果表明,随着水凝胶中SF含量的增加,膨胀率增大,压缩强度减小,药物释放速率加快,且PAAS-SF20 semi-IPN水凝胶在120 h内能释放(83.4±0.9)%的药物.所开发的自膨胀PAAS-SFsemi-IPN水凝胶具有高膨胀率和良好的药物释放能力,将在药物输送或其它植入材料领域有良好的应用前景.     

BaCe0.5Zr0.4Y0.1O3-δ粉体的溶胶-凝胶法和高温固相法制备及性能表征

分别通过溶胶-凝胶法和高温固相反应法制备了BaCe0.5Zr0.4Y0.1O3-δ粉体.采用热重-差热分析(TG-DTA),粉末X射线衍射(XRD),扫描电子显微镜(SEM),傅立叶红外衍射(FT-IR),N2吸附-脱附等方法对所制备的粉体进行了表征.结果表明:用溶胶-凝胶法在1200 ℃×10 h可以合成纯的BaCe0.5Zr0.4Y0.1O3-δ粉体,合成温度比传统的高温固相反应法降低400 ℃左右;溶胶-凝胶法合成粉体具有多孔结构特征,与固相法合成粉体相比具有较高的比表面积.但致密化试验表明:溶胶-凝胶法合成粉体与固相法合成粉体相比具有较低的烧结活性.溶胶-凝胶法合成粉体颗粒表面残余的有机基团和颗粒内部的大量微孔将在致密化过程中产生空间位阻,从而影响高温下原子的迁移,阻碍材料的致密化过程.     

酸敏感型嵌段共聚物mPEG-acetal-PIB的合成、表征及用于构筑水凝胶敷料

利用点击化学(“Click”)反应, 成功制备了一种通过酸敏感缩醛基团键合的两亲性嵌段共聚物, 聚乙二醇单甲醚-acetal-聚异丁烯(简写为mPEG-acetal-PIB). 通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)和凝胶渗透色谱(GPC)对聚合物的结构、分子量及分子量分布进行表征. 利用芘荧光探针法、动态激光光散射(DLS)和透射电子显微镜(TEM), 研究共聚物在水溶液中组装的临界聚集浓度(CAC), 胶束的粒径大小、分布以及形貌. 利用DLS跟踪测试聚合物胶束在酸性条件下的粒径变化, 验证mPEG-acetal-PIB的酸敏感性质. 随后, 在体系中引入α-环糊精(α-CD), 诱导形成超分子水凝胶. 利用X射线衍射(XRD)分析PEG与α-CD的包结络合作用, 流变仪测试水凝胶的凝胶化时间和黏弹性. 通过体外细胞毒性试验(MTT法)证明嵌段共聚物mPEG-acetal-PIB及水凝胶均具有良好的生物相容性. 这种水凝胶能够保持创面湿润, 具有温和的冷却作用, 并且由于其带有酸敏感基团, 能够在偏酸性环境降解, 减少炎症发生率, 在水凝胶创伤敷料中具有潜在的应用.     

超快速溶胶-凝胶法制备高纯二氧化硅单块＊

An ultra-fast sol-gel process has been developed to get high content silica materials,in which,the solvent tetrahydrofuran(THF) for hydrolysis of precursor tetraethyl orthosilicate,was removed through solvent extraction to obtain bulk sol.The bulk sol can be molded in different shapes such as discoid,pellet,octagon,cylinder,and half-sphere.They solidified and gelled in a very short time in the presence of lithium salt.Measurements show that the silica monoliths possess volume shrinkage of 52%,high silica content of 82.4% and transmittance of 70% in the UV/Vis region,and are crack-free indefinitely.     

Synthesis of nanoporous silica aerogel by ambient pressure drying

A crack-free silica aerogel monolith was fabricated from a cheap water glass derived silicic acid solution by adding glycerol, which served as a drying control chemical additive (DCCA). The OH surfaces of the wet gel with glycerol were modified using a TMCS/n-hexane mixture followed by solvent exchange from water to n-hexane. The obtained surface modified wet gel was dried at 75 °C under ambient pressure. The addition of glycerol appears to give the wet gel a more homogeneous microstructure (larger pore size and uniform size distribution) as well as enhanced stiffness. However, glycerol also retards surface modification and solvent exchange. The aerogel synthesized with glycerol added to the silica sol maintained a relatively low bulk density compared with the aerogels aged in a mixed ethanol (EtOH)/TEOS solution. The reproducibility of aerogel production was further improved in the aerogel synthesized with glycerol added to the silica sol and aged in a 70%EtOH/30%TEOS solution.     

Template-free sol–gel synthesis of high surface area mesoporous silica based catalysts for esterification of di-carboxylic acids

High surface area mesoporous silica based catalysts have been prepared by a simple hydrolysis/sol–gel process without using any organic template and hydrothermal treatment. A controlled hydrolysis of ethyl silicate-40, an industrial bulk chemical, as a silica precursor, resulted in the formation of very high surface area (719 m²/g) mesoporous (pore size 67 Å and pore volume 1.19 cc/g) silica. The formation of mesoporous silica has been correlated with the polymeric nature of the ethyl silicate-40 silica precursor which on hydrolysis and further condensation forms long chain silica species which hinders the formation of a close condensed structure thus creating larger pores resulting in the formation of high surface mesoporous silica. Ethyl silicate-40 was used further for preparing a solid acid catalyst by supporting molybdenum oxide nanoparticles on mesoporous silica by a simple hydrolysis sol–gel synthesis procedure. The catalysts showed very high acidity as determined by NH₃-TPD with the presence of Lewis as well as Brønsted acidity. These catalysts showed very high catalytic activity for esterification; a typical acid catalyzed organic transformation of various mono- and di-carboxylic acids with a range of alcohols. The in situ formed silicomolybdic acid heteropoly-anion species during the catalytic reactions were found to be catalytically active species for these reactions. Ethyl silicate-40, an industrial bulk silica precursor, has shown a good potential for its use as a silica precursor for the preparation of mesoporous silica based heterogeneous catalysts on a larger scale at a lower cost.     

Patterning of sol gel thin films by capillary force assisted soft lithographic technique

Patterning of sol gel based silica and silica–titania films has been developed at room temperature by soft lithographic technique. Corresponding metal alkoxides have been utilized for the preparation of precursor sols. Elastomeric stamps of polydimethylsiloxane (PDMS) are used to emboss patterns of a master grating on the as-prepared silica and silica–titania films obtained by sol gel process. Pressure-less capillary force lithography has been used to fabricate both 1-D and 2-D ordered structures of simple stripe patterns. A modified solvent assisted lithography and micro-molding in capillaries yielded stable and high fidelity 1-D structures for silica and silica–titania films over a large area.     

Preparation and properties investigation of PMMA/silica composites derived from silicic acid

Hybrid materials based on silicic acid and polymethyl methacrylate (PMMA) were prepared by in situ bulk polymerization of a silicic acid sol and MMA mixture. Silicic acid sol was obtained by tetrahydrofuran (THF) extraction of silicic acid from water. Silicic acid was prepared by hydrolysis and condensation of sodium silicate in the presence of 3.6 M HCl. As a comparative study, PMMA composites filled by silica particles, which were derived from calcining the silicic acid gel, were prepared by a comparable in situ polymerization. Each set of PMMA/silica composites was subjected to thermal and mechanical studies. Residual THF in PMMA/silicic acid composites impacted the properties of the polymer composites. With increase in silica content, the PMMA composites filled with silica particles showed improved thermal and mechanical properties, whereas a decrease in thermal stability and mechanical strength was found for PMMA composites filled with silicic acid dissolved in THF. With a better compatibility with polymer matrix, silicic acid sol shows better reinforcement than silica particles in PMMA films prepared via blending of the corresponding THF solutions. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and characteristics of spinnable sol and continuous mullite fibers with nano silica addition

The spinning precursor sols for the continuous mullite-based fibers were prepared by adding nano-silica to substitute part of silica sol. The effect of SiO₂ nanoparticles on the particle evolution models, polymerization degree and solid content of the sol,and the spinning length and sintering behavior of the fibers was investigated. The results were shown that the addition of nano silica enhanced the polymerization degree and extended the spinnable range of the sol. The appropriate polymerization degree (B value) for this sol system was 1.885–2.145. The grain diameter decreased from 39.6 to 25.9 nm with increasing the nano-silica content to 20 %, and then, it increased to 41.2 nm with increasing the nano-silica content to 100 %. The appropriate content of nano-silica powders would reduce the grain diameter. However, it had no influence on the linear growth model, homogeneity and solid content of the precursor sol.     

Synthesis of monodispersed silica nanoparticles with high concentration by the Stöber process

Silica nanoparticles with high concentration were prepared by the sol–gel process based on the Stöber method using tetraethoxysilane as a starting material. It was found that silica sol with about 4 wt% in concentration and with a diameter of about 10 nm was obtained by controlling the reaction conditions in the Stöber process. By removing the solvent under a reduced pressure, the particle concentration was increased up to 15 wt% without aggregation.     

Effect of sepiolite fiber on the structure and properties of the sepiolite/silica aerogel composite

Sepiolite fiber-reinforced silica aerogel composites for thermal insulators were prepared by dispersing sepiolite fiber in silica sol, aging, solvent exchanging, and drying in supercritical fluid. The surface treated sepiolite fiber and sepiolite/silica aerogel composite were characterized by scanning electron microscope; transmission electron microscope and Fourier transform infrared spectroscopy. The influence of surface treated sepiolite fiber on the mechanical and thermal properties of the aerogel composite was studied. The results indicate the hydroxyl groups on silica sol particles surface able to condense with the hydroxyls of sepiolite fibers with forming Si–O–Si between sepiolite fibers and aerogel matrix in the sol–gel process, which achieves excellent interfacial interaction in the sepiolite/silica aerogel composite, so the mechanical properties of the aerogel composite have been improved effectively without sacrificing much thermal insulating performance.     

整体式催化剂活性组分负载策略及微波催化燃烧甲苯特性

针对催化剂活性组分脱落问题，采用载体预处理和添加硅溶胶的策略来强化活性组分负载，微波单模腔中催化燃烧甲苯以考察催化剂活性，并对牢固负载的催化剂进行表征分析。研究表明，常温下采用10%盐酸溶液对蜂窝状堇青石（CH）载体预处理、硅溶胶添加量与载体吸水量比值为0.125条件下所制备的Cu-Mn-Ce（硅溶胶）/CH催化剂脱落率为0.0129%，明显低于Cu-Mn-Ce/CH催化剂的0.950%。Cu-Mn-Ce（硅溶胶）/CH催化剂具有更小的活性颗粒尺寸、更大的比表面积和更多样的活性晶体，在甲苯进气浓度1000 mg/m³、进气量0.12 m³/h、微波功率200 W和床层温度350℃条件下，催化剂对甲苯的催化燃烧效率和矿化率分别为98.5%和87.9%；连续实验43 h后，催化剂活性保持稳定且活性组分脱落率低（0.0328%）。硅溶胶的添加增强了活性组分与载体之间的相互作用力，生成的硅氧烷化学键提高了活性组分的结合牢固度。     

Effective preparation of crack-free silica aerogels via ambient drying

Effective ambient-drying techniques for synthesizing crack-free silica aerogel bulks from the industrial waterglass have been developed. Silica wet gels were obtained from aqueous colloidal silica sols prepared by ion-exchange of waterglass solution (4–10 wt% SiO₂). Crack-free monolithic silica aerogel disks (diameter of 22 mm and thickness of 7 mm) were produced via solvent exchange/surface modification of the wet gels using isopropanol/trimethylchlorosilane/n-Hexane solution, followed by ambient drying. The effects of the silica content in sol and the molar ratio of trimethylchlorosilane/pore water on the morphology and property of final aerogel products were also investigated. The porosity, density, and specific surface area of silica aerogels were in the range of 92–94%, 0.13–0.16 g/cm³, and ∼675 m²/g, respectively. The degree of springback during the ambient drying processing of modified silica gels was 94%.