单分散二氧化硅微球的制备及表面化学修饰

采用St(o)ber法在醇-水混合体系中,以正硅酸乙酯(TEOS)作为硅源,在氨水催化作用下制备SiO2纳米微球,分析了不同浓度的氨水、TEOS、乙醇和温度对SiO2微球形貌及粒径的影响,并利用透射电镜对其形貌和粒径进行表征.最后引入具有疏水基团的十六烷基三甲氧基硅烷对SiO2微球表面进行修饰,并采用FT-IR和测量接触角对修饰的SiO2微球进行分析.结果表明:SiO2微球粒径随氨水浓度的增加而增大;随TEOS、乙醇浓度和温度的升高先增大后减小;并通过FT-IR和测量接触角证明疏水基团成功接枝到SiO2微球表面.     

乙烯基三甲氧基硅烷对二氧化硅的超疏水改性研究

采用乙烯基三甲氧基硅烷(VTMO)为改性剂,以氨水为pH调节剂制备改性二氧化硅(SiO2)超疏水材料.通过CA、FTIR和SEM对材料接触角、组成和形貌进行表征.考察了VTMO与SiO2的比例、反应时间、干燥时间对改性二氧化硅超疏水材料接触角和形貌的影响.结果表明,VTMO可在较短时间内改性二氧化硅制备出超疏水二氧化硅粉体,VTMO与SiO2比例对改性SiO2粉体的水接触角和微观二重结构有明显影响,而反应时间和干燥时间的影响较小.     

SiO2粉体制备及其与Ag2S复合工艺研究

采用改性Stober法来可控制备SiO2粉体,并探究了不同沉淀剂对SiO2粉体形貌及粒径大小的影响.分别采用水热法、溶剂热法和沉淀法来制备SiO2/Ag2S复合粉体,并使用XRD、SEM-EDS、NanoMeasure等手段对制备出的各种粉体的物相、成分、形貌和粒径分布等进行表征与分析.结果表明,以正硅酸乙酯(TEOS)为硅源,氨水为沉淀剂时,添加适量聚丙烯酸酯乳液可有效控制SiO2微球的粒径;以碳酸钠水溶液为沉淀剂时,能得到线状SiO2粉体.在140 ℃下水热处理6 h得到的SiO2/Ag2S粉体的复合效果较好;常温下,通过热处理共沉淀出的SiO2/Ag2S粉体具有操作简便、反应条件易控制、复合效果较好等优点.     

静电纺丝法制备超疏水/超亲油SiO2微纳米纤维膜

采用静电纺丝法制备SiO2微纳米纤维膜,经六甲基硅氮烷(HMDS)改性后获得疏水/亲油特性,用FTIR、SEM、接触角等手段表征纤维膜的成分、微观形貌和对水及正十二烷的润湿性能等,研究了制备工艺对纤维膜物性参数以及润湿性能的影响,并测试了改性后纤维膜的高温稳定性和耐腐蚀性能.结果表明:SiO2微纳米纤维膜具有较多的孔隙和较高的比表面积,经HMDS改性后其表面粗糙结构结合疏水亲油的-Si(CH3)3基团使得纤维膜获得超疏水/超亲油特性,其水接触角为153.7°、水滚动接触角为8.2°、油接触角为0°;超疏水/超亲油SiO2微纳米纤维膜的最高耐受温度为450℃,最大拉伸强力为(40.7 ±9.4)×10-2N,且具有较好的耐腐蚀性能.     

利用不同硅前体制备超疏水性白炭黑膜

以稻壳灰和水玻璃为前驱体,以氨基硅油(amino silicon oil-ASO)为改性剂,采用溶胶-凝胶法制备不同性能的超疏水性白炭黑及其膜.主要研究不同前驱体和改性剂用量对白炭黑疏水性膜性能的影响,通过扫描电子显微镜、傅里叶变换红外光谱仪和润湿接触角进行性能表征.研究结果表明,以稻壳灰或水玻璃为前驱体,采用改进的溶胶-凝胶法均能制备出接触角大于160°的SiO2超疏水膜;采用相同的改性剂,可以得到颗粒形态完全不同的SiO2膜;改性剂的作用对SiO2表面改性作用是一种接枝反应,将疏水性基团接枝替代SiO2表面的羟基,而使SiO2表面疏水,且能起到模板作用,引导水玻璃溶胶颗粒聚合成棒状或纤维状结构.     

空心和实心SiO2胶体晶体微球的快速制备方法

胶体晶体微球因其独特的内部结构被广泛地应用到诸多领域.本文提供了一种简单、快速合成SiO2胶体晶体微球的方法,即:将单分散SiO2微球悬浮液加入到有机溶剂(正辛醇或二甲基硅油)中超声乳化,使SiO2微球在溶剂中自组装,形成SiO2胶体晶体微球,用扫描电镜(SEM)观察其形貌结构,用Nano Measurer 1.2软件统计其粒径分布.实验表明,SiO2胶体晶体微球在正辛醇中形成空心结构,在二甲基硅油中形成实心结构;悬浮液浓度,悬浮液与溶剂的质量比,单分散SiO2微球粒径不会明显影响SiO2胶体晶体微球的形貌和结构,但会对其粒径分布产生一定的影响.     

超声辅助沉淀法制备疏水性纳米SiO2

采用超声沉淀法制备出SiO2纳米粉体,利用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对其进行了表面改性,并利用红外光谱(FT-IR)、热重(TG)、接触角、透射电镜(TEM)等方法对SiO2的结构和性能进行了表征,并研究了KH-570用量和改性时间对SiO2活化指数的影响。结果表明:与普通搅拌相比,超声更利于纳米SiO2的制备和改性。超声条件下,KH-570成功接枝到SiO2纳米粒子的表面。且改性后的SiO2疏水性提高,在无水乙醇中的分散状态得到明显改善。当改性剂用量为6 mL,改性时间为1 h时,SiO2纳米粒子的活化指数达到100%。     

以稻壳灰为硅源制备超疏水性白炭黑

以稻壳为原料,采用自蔓延燃烧法制备高活性的稻壳灰.以稻壳灰为原料,采用碱溶煮-酸反应法制备较高纯度的白炭黑.以六甲基二硅氮烷(HMS)为改性剂,采用溶胶-凝胶法制备超疏水性的白炭黑及其膜.主要研究酸反应过程中的pH值和反应时间对白炭黑中SiO2含量的影响,以及六甲基二硅氮烷改性剂对白炭黑(SiO2)膜疏水性能的影响,通过XRD、SEM、IR和润湿接触角进行性能表征.研究结果表明,将稻壳灰在NaOH溶液中加热到90℃后溶煮2h,再用硫酸调节溶液的pH值为3,反应时间控制在2h时,白炭黑SiO2的含量可达98.48;.当六甲基二硅氮烷用.量为0.15(与硅钠溶液的质量之比)时,可以获得接触角为166.3.的SiO2的SiO2超疏水膜.而改性剂对SiO2表面改性作用是一种接枝反应,将疏水性基团接枝替代SiO2表面的羟基,而使SiO2表面疏水.     

Si69有机湿法改性白炭黑及其性能表征

以Si69为改性剂,无水乙醇为溶剂,设计正交试验,对沉淀法白炭黑粉体进行有机湿法改性,探究实验最佳工艺.采用X射线衍射、傅里叶红外光谱、热失重分析仪、接触角仪、纳米粒度及Zeta电位仪、扫描电镜等对改性前后白炭黑的结构形貌及其性能进行表征,主要考察了Si69改性剂对沉淀法白炭黑的疏水性及分散性的影响.结果表明:实验的最佳工艺为反应温度55℃,反应时间4h,pH值为7.当Si69用量为0.375 g时,改性白炭黑的分散性最好.改性后的白炭黑仍为无定形态,物相结构没有变化;改性过后的白炭黑其表面羟基数减小,疏水性增强,接触角由改性前的9°增大到97°;改性使白炭黑表面极性减弱,粒径分布变窄,降低了颗粒团聚程度,分散性得到明显提高.     

白炭黑的长链烷基官能化改性及表征

以正二十二醇为改性剂对沉淀法白炭黑粉体进行了表面改性.采用傅里叶红外光谱(FTIR)、热重(TG)、元素分析(EA)、接触角仪、激光粒度分布分析、透射电镜(TEM)等表征手段,研究考察了长链烷基对沉淀法白炭黑形貌及性能的影响.结果表明:正二十二醇成功接枝到了白炭黑的表面,且每克白炭黑表面接枝改性剂的量为0.0328 mol/g;改性后白炭黑的分散性和疏水性得到明显提高,其接触角由改性前的0°增加到了132°;改性后的白炭黑粉体粒径分布变窄,粒子平均粒径值由改性前的491.2 nm减小到240 nm.     

HNTs/SiO2复合气凝胶制备及其性能研究

采用正硅酸乙酯(TEOS)为硅原,以硅烷改性的埃洛石纳米管(HNTs)为增强相,利用CO2超临界干燥技术制备具有优良力学和隔热性能的HNTs/SiO2复合气凝胶.利用傅立叶红外光谱、扫描电镜、比表面积与孔径分析仪、万能试验机和导热率测量仪等手段对HNTs改性后的表面状态、HNTs/SiO2复合气凝胶的微观形貌、孔结构、力学和导热性能进行了测试分析.结果表明:改性后的HNTs均匀分散到二氧化硅气凝胶基体中,并与SiO2纳米颗粒实现良好的结合,HNTs/SiO2复合气凝胶呈三维网络结构,当HNTs含量为15wt;时,平均孔径为10.47 nm;随着HNTs含量的增加,复合气凝胶的力学性能不断增强,同时其导热系数也不断增大,当HNTs含量为15wt;时,HNTs/SiO2复合气凝胶的抗压强度为0.85 MPa,导热系数为0.024 W/mK.     

Mechanical and thermal properties of SiO2–PMMA monoliths

Organic–inorganic hybrid monoliths of cross-linked polymethylmethacrylate (PMMA) and silica (SiO₂) were prepared by sol–gel, using tetraethoxysilane (TEOS) and methylmethacrylate (MMA) as precursors and 3-(trimethoxysilyl) propylmethacrylate (TMSPM) to make compatible the organic and inorganic components. Two types of monoliths were prepared, H1-type using a molar ratio composition of 16:1:4 for water:TEOS:ethanol and 1:0.1:0.1 for TEOS:TMSPM:MMA and H2-type using 6.3:1:2.52 for water:TEOS:ethanol and 1:0.25:0.25 for TEOS:TMSPM:MMA. Semi-transparent monoliths were obtained in both cases after the gelation–solidification and drying processes, which took about seven days. Thermal properties of the samples were obtained by applying thermal lens spectroscopy and their mechanical properties were measured by depth sensing indentation and Vickers microhardness. FTIR spectroscopy measurements were performed to complement the characterization. We found that the hardness of the hybrid monoliths have values between those of commercial PMMA and a sol–gel SiO₂ monolith. This result is a consequence of the reinforcement produced by the SiO₂ component in the organic–inorganic hybrid matrix. The thermal diffusivity of the hybrid monoliths shows an appreciable increasing in the hybrid system with respect to the pure SiO₂ monolith. Mechanical behavior of monoliths is strong influenced by the SiO₂–PMMA ratio or changing the water:TEOS:ethanol contents.     

改性羟基磷灰石晶须牙科复合树脂材料的制备及研究

采用硅胶对制备的HAP晶须进行表面改性形成SiO2颗粒附着,然后以硅胶改性的HAP晶须为填料混合甲基丙烯酸酯制备复合树脂材料.二氧化硅对晶须改性是通过形成凝胶颗粒与晶须结合并通过热处理形成牢固的结合.通过XRD、FT-IR光谱和SEM以表征微结构、键性质以及表面相组成.结果表明:经硅胶改性的HAP晶须表面有SiO2小颗粒附着,随着煅烧温度的增加,SiO2颗粒的数量明显增多,尺寸有变大的趋势.复合树脂材料的弯曲强度随改性晶须煅烧温度的增加而增加,以600 ℃煅烧的改性晶须为原料制备的树脂样品,其弯曲强度最高,达到89.46 MPa.     

Silica xerogels of tailored porosity as support matrix for optical chemical sensors. Simultaneous effect of pH, ethanol:TEOS and water:TEOS molar ratios, and synthesis temperature on gelation time, and textural and structural properties

The sensing of a chemical environment is achieved mainly in the surface by interactions of the sensor material with its chemical surroundings. Therefore, porous structure control is key in developing good chemical sensors. The aim of this work was to obtain materials of tailored porosity to be used as support matrix for optical chemical sensors. We studied the simultaneous effect of pH, temperature, ethanol:TEOS, and water:TEOS molar ratios on gelation time, and textural and structural properties. We used a 2⁴ factorial design that evaluates the effect of each independent variable and their interactions. Samples were characterized by XRD, SEM, FTIR, and gas adsorption (N₂ at 77 K and CO₂ at 273 K). The gelation time decreased with increasing temperature, water:TEOS molar ratio, and pH; and with decreasing ethanol:TEOS molar ratios. Synthesis conditions also affected the xerogels porous textures. Xerogels obtained at pH 2.5 were ultramicroporous. In general, samples synthesized at pH 4.5 and ethanol:TEOS molar ratio of 2.25:1 were mesoporous, but the material is not appropriate for use as support in fiber optical sensors.     

Effects of dimethyldiethoxysilane addition on the sol-gel process of tetraethylorthosilicate

The effects of dimethyldiethoxysilane (DDS) addition on the sol-gel process of tetraethylorthosilicate (TEOS) were investigated by varying the addition-time of DDS to acid-catalyzed TEOS solutions in different water contents. At a low water content, the solution is transparent until gelation takes place, while at a high water content, phase separation occurs and leads to hydrophobic particles which, according to scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and thermogravimetric (TG) analysis, show different morphology and thermal behavior. The reaction between TEOS and DDS in different water contents and the structure of final polymers are discussed.     

Synthesis,transformation to octahedron‐like crystals,and gas‐sensing property of six‐horned nanospheres of Cu2O

Single‐crystal six‐horned nanospheres of Cu₂O with a diameter of 760 nm in average were prepared in aqueous solution of CuCl₂and NaOH by using ascorbic acid as the reductant in the presence of sodium dodecyl benzenesulfonate (SDBS) at room temperature. The horn grows along the <100> direction, which is consistent with the protuberant direction of an apex of octahedron. The formation process of six‐horned nanospheres included two steps: the formation of Cu₂O nanospheres via Ostwald ripening process, and the appearance of horns on the surface of nanospheres under low concentration of SDBS. As increasing the concentration of SDBS, the six‐horned nanospheres could be transformed into octahedron‐like Cu₂O. And at the same concentration of SDBS, keeping the volume ratio of water and ethanol in mixed solutions as 1:1, Cu₂O octahedra were obtained. Moreover, gas‐sensing property showed that six‐horned nanospheres of Cu₂O had higher sensitivity compared with Cu₂O nanospheres and Cu₂O octahedra to ethanol gas (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Shrinkage behavior of silica gels during drying

The shrinkage behavior during drying has been studied for silica gels prepared from a mixture of TEOS, water and ethanol. Significant differences in the shrinkage were noted between base- and acid-catalyzed gels after that the volumes shrank to about 40% of the initial value. The volume shrinkage was also affected by the alcohol/water ratio of the pore liquid. The gel had a tendency to shrink still more with increasing water concentration in the liquid. On the other hand, the higher the alcohol content of the pore liquid, the lower the bulk density of the dried gel. SEM pictures illustrate that both base- and acid-catalyzed gels have granular structures consisting of particles of similar size initially and, when dried, the packing state of the gel particles are different, depending on catalysis for the hydrolysis-polymerization and alcohol/water ratio of the pore liquid.     

Morphology control of MSU-1 silica particles

Mesoporous silica, MSU-1 with spherical morphology was prepared using TEOS (tetraethylorthosilicate) as a silica source in the presence of an alkyl polyethylene oxide surfactant via the novel two-step process proposed by Prouzet’s group: hydrolysis of TEOS conducted in highly acidic condition at room temperature followed by condensation promoted by fluoride salt addition at 35 °C. The particles produced were characterized by XRD, SEM, and N₂ adsorption/desorption isotherm. Static condensation period was found to be essential to have spherical morphology. Growth of spherical particles and evolution of porosity were studied as a function of time, temperature, NaF/TEOS, and TEOS/surfactant ratio. The MSU-1 particles prepared under different synthesis conditions were briefly tested for chromatographic separation of selected organic molecules, which demonstrates the governing influence of the pore size in MSU-1 on retention time.     

硅酸锶粉体的溶胶-凝胶制备工艺及机理

以正硅酸乙酯(TEOS)和Sr(NO3)2为原料,采用溶胶-凝胶法制备出高纯度的不规则形状硅酸锶粉体。利用X射线衍射仪、扫描电镜和差热-热重分析仪等研究了锶盐种类、水硅比和pH值对硅酸锶粉体的相结构、形貌和纯度的影响,探讨了溶胶-凝胶法制备硅酸锶粉体的反应过程与机理。结果表明:溶胶-凝胶法制备Sr2S iO4粉体的最佳工艺条件为:锶盐选择Sr(NO3)2,n(H2O)∶n(TEOS)∶n(EtOH)为24∶1∶5,pH值为3~4,煅烧温度为800℃。与传统高温固相反应法相比,该方法大幅度降低了煅烧温度,提高了粉体的纯度,同时能够减小最终获得的硅酸锶粉体粒径。     

Chemical reaction kinetics leading to the first Stober silica nanoparticles – NMR and SAXS investigation

²⁹Si-NMR and ¹³C-NMR were used in methanol and ethanol to monitor the intermediates or hydrolyzed monomers that lead to the formation of the first primary particles as detected by small angle X-ray scattering. This identification was facilitated by using initial NH₃ and H₂O levels at the lower end of those experienced in Stober synthesis to slow the reaction kinetics. We found that [NH₃] and [H₂O] control the balance between hydrolysis of tetraethylorthosilicate (TEOS) and the condensation of its hydrolyzed monomers. Transesterification between methanol and TEOS did occur; however, it was negligible compared to the production of hydrolyzed intermediates. The first nanostructures appear at a hydrolyzed monomer concentration around 0.1 M, indicating that formation of the primary structures is thermodynamically controlled by a supersaturation of the intermediate species. Differences in particle size between methanol and ethanol are attributed to thermodynamic interactions between the solvent and the hydrolyzed intermediates.