Architecture of colloidal crystals constructed by silica hybrid nanoparticles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter D_n = 192 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brushes encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization (ATRP) approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. We constructed the colloidal crystals using these photofunctional particles. Moreover, the SiO₂ particle array of colloidal crystals was locked by radical photopolymerization with vinyl monomer as a matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

硅烷偶联剂改性玻璃纤维增强硅气凝胶的研究

为了达到增强硅气凝胶力学性能的目的,采用硅烷偶联剂KH550与KH560二步改性接枝玻璃纤维,进而制备纤维增强硅气凝胶。利用扫描电子显微镜、红外光谱仪、比表面及孔径分布仪、热重-差热分析仪、导热系数仪、电子动静态疲劳试验机等对其表征。实验结果表明：硅烷偶联剂改性玻璃纤维与硅气凝胶复合后网络结构更加均匀、骨架强度更加稳定、孔径多在30 nm以下、具有良好的热稳定性;同时,改性玻璃纤维的最佳添加量为20%（质量分数）,此时其密度为0.167 g/cm³,导热系数为0.018 5 W/（m·K）,接触角为127°,抗弯强度为1.042 MPa,抗压强度为0.669 MPa,达到预期实验目的。     

偶联剂对白炭黑／SBR复合材料力学性能的影响

研究了4种偶联剂KH-550、KH-792、WD-60和HG-305对白炭黑／SBR复合材料力学性能和热空气老化性能的影响。研究结果表明：当KH-550用量为4．0份时,复合材料的综合力学性能最好,与未改的白炭黑／SBR复合材料相比,其拉伸强度和撕裂强度分别提高了77％和24％;复合材料的老化实验结果表明,经偶联剂改性的复合材料的耐热老化性能有所下降,其中HG-305改性的复合材料抗老化性较好。     

Synthesis and characterization of polyimide/silica hybrid nanocomposites

Polyimide/silica (PI/SiO₂) hybrid nanocomposites were prepared by the sol‐gel process directly from a soluble polyimide. This soluble PI was synthesized from a diamine with a pendant phenyl hydroxyl group, 4,4′‐diamino‐4″‐hydroxy triphenyl methane (DHTM) and a dianhydride, pyromellitic dianhydride (PMDA), followed by cyclodehydration. Three ways of preparing PI/SiO₂ hybrid nanocomposites were investigated in this study. Two of them used the coupling agent 3‐glycidyloxy propyl trimethoxysilane (GPTMOS) to enhance the compatibility between PI and silica. The coupling agent can react with the PI to form covalent bonds. The structures of the modified hybrid nanocomposites were identified with a FTIR, whereas the size of the silica in polyimides was characterized with a scanning electron microscope. The size of silica particles in the modified system was <100 nm. The covalently bonded PI/SiO₂ hybrid nanocomposites prepared by the novel third approach exhibited good transparency when the silica content was <15%. Moreover, their thermal and mechanical properties exhibited a significant improvement. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 382–393, 2004     

纳米杂化有机硅溶胶在金属防腐中的应用

以四乙氧基硅烷与一些有机硅氟烷为原料,通过溶胶-凝胶法,在催化剂和加热条件下制备出醇基纳米杂化有机硅溶胶。研究了它们的水接触角。结果发现,当n(MTES)∶n(TEOS)=4∶1时,涂膜的疏水性最好。以疏水性强的前驱体DMDES、OTES和12FHPTMS对该纳米杂化有机硅溶胶进行改性,所得涂膜的疏水性能明显增强。采用IR对涂膜进行了表征。电镜照片显示,硅溶胶颗粒粒径为60～100nm。研究了涂膜的理化性能。结果表明,涂膜的疏水性强,硬度9H,附着力1级,冲击强度达500N·cm以上。其中,成本最低的涂膜,也具有较好的耐蚀、耐污和抗洗刷性。     

Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process

Colloidal silica particles are prepared via a sol gel technique carried out in an inverse microemulsion of water in a toluene solution of tetraethoxysilane (TEOS), stabilized by either an anionic surfactant AOT or isopropanol. Functionalized material was obtained using a functional coupling agent (RO)₃Si(CH₂)₃ X, X being a functional group such as methacryloyl, thiol, vinyl, amino group, or a chlorine atom. Functionalization can be carried out either directly via the direct copolycondensation of TEOS and the coupling agent, or in a two-step process involving a core-shell polycondensation of the coupling agent onto preformed silica particles. Kinetic studies of the copolycondensation are carried out using either²⁹Si NMR analysis or liquid chromatography. They show that the consumption of TEOS is more rapid than that of the coupling agent. The materials are characterized both chemically (elemental analysis, FTIR,¹³C and²⁹Si NMR CPMAS analysis), and by their particle size. The silica functionalized with a polymerizable methacryloyl group is encapsulated by a polymer layer in an inverse emulsion polymerization of acrylic acid. After inversion of the emulsion in water, the resulting material is covered with a layer of hydrophobic polymer in a conventional emulsion polymerization.     

二氧化硅表面修饰硅烷偶联剂APTS的过程和机制

二氧化硅表面经过硅烷偶联剂γ-氨丙基三乙氧基硅烷（APTS）修饰后,在橡胶、塑料、催化剂、色谱柱、吸附剂、生物和医药等领域中具有独特的应用性能,大量文献结合特定应用体系研究二氧化硅表面修饰APTS的基本规律,以实现理想可控的修饰效果。总结这些分散性研究结果,有利于在新的基础上有效地促进研究的深入。在分析文献的基础上,系统地阐述了二氧化硅表面修饰APTS的反应机理、修饰工艺、反应动力学、修饰层稳定性和结构形貌等方面的研究进展,提出了目前研究还存在的问题和进一步的研究方向。     

Preparation and thermal properties of epoxy-silica nanocomposites from nanoscale colloidal silica

Epoxy-silica nanocomposites were obtained from directly blending diglycidylether of bisphenol-A and nanoscale colloidal silica and then curing with 4,4-diaminodiphenylmethane. The epoxy-silica nanocompoites showed good transparency and miscibility observed with AFM, SEM, and TEM. The thermal stability of the epoxy resins was improved with the incorporation of the colloidal silica. However, a depression on the glass transition temperature of the resins was observed, owing to the plasticizing effect of the colloidal silica. Moreover, the nanoscale colloidal silica did not show effectively synergistic effect on char formation and flame retardance with phosphorus.     

Reinforcement of Styrene-Butadiene Rubber with Silica Modified by Silane Coupling Agents Experimental and Theoretical Chemistry Study

The properties of styrene-butadiene rubber （SBR） reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized geometries of molecular modified silica reinforced SBR were obtained by using B3LYP calculation of density functional theory with the 6-31＋G basis sets. The natural bond orbital analyses were carried out. The Si-O bond length of silica modified by KH-792 was the shortest and the electronegative of O was the highest. It indicated that the connection between silica and KH-792 was the tightest. Higher tensile strength and elongation of reinforced SBR was obtained by silica modified with the KH-792. It was caused by large delocalization of lone pair electrons of the two N atoms in KH-792. The S-C bond length in silica modified by KH-590 was longer than the ordinary S-C bond length. Then the sulfur free radical （·S·） was produced more easily in vulcanization. The degree of crosslink was increased by the cross-linkage of the rubber molecule and the sulfur free radical. That was why the highest stress and tear strength of reinforced SBR was produced when silane coupling agent KH-590 was used. The calculation results was in accord with experimental data.     

In situ emulsion polymerization and characterization of PVAc nanocomposites including colloidal silica nanoparticles for wood specimens bonding

Polyvinyl acetate (PVAc) nanocomposites for wood adhesives containing different amounts of colloidal silica nanoparticles (CSNs) were synthesized via in situ one-step emulsion polymerization. The adhesion strength of wood specimens bonded by PVAc nanocomposites was investigated by the tensile test. Thermal properties of PVAc nanocomposites were also characterized by differential scanning calorimetry and thermogravimetric analysis. Rheological and morphological properties of the PVAc nanocomposites were investigated using rheometric mechanical spectrometry and field emission scanning electron microscopy (FESEM), respectively. The obtaining results showed that the shear strength of PVAc nanocomposite including 1 wt. % CSNs has the highest shear and tensile strength about 4.7 and 3.2 MPa, respectively. A small increment of T_g (~3 °C) and considerable increment of the ash content proved the enhancement of PVAc thermal characterization in the presence of CSNs. FESEM results showed uniform dispersion of nanoparticles throughout the PVAc matrix due to using the in situ emulsion polymerization process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48570.     

橄榄石酸溶制备超细二氧化硅改性研究

橄榄石酸溶制备超细二氧化硅工艺简单、生产成本低。但是制备的超细二氧化硅表面羟基键合严重、分散性能差、易团聚。利用硅烷偶联剂对橄榄石酸溶制备的超细二氧化硅进行改性研究。采用单因素实验考察了硅烷偶联剂品种、改性时间、改性温度及改性剂用量等因素对超细二氧化硅改性效果的影响。实验结果表明,在硅烷偶联剂KH-550加入量为6 mL/g、改性时间为5 h、改性温度为75 ℃条件下,制备的超细二氧化硅表面的羟基数量减少至2.08×10 ²⁰ 个/g、接枝率为8.35%、接触角达到101.51°,极大地提高了超细二氧化硅的表面疏水性。     

硅烷偶联剂改性环氧丙烯酸酯的合成与应用

针对环氧丙烯酸酯附着力和柔韧性差的缺点,通过在环氧丙烯酸酯中引入硅烷基团,合成硅烷改性的环氧丙烯酸酯。考察了各工艺参数对反应产品的影响,通过滴定和红外光谱分析跟踪反应进程和确定产物结构。合成产物通过和光固化单体、光引发剂混配成紫外光固化胶粘剂,并与改性之前的环氧丙烯酸酯作为主体树脂时的紫外光固化胶粘剂的性能进行了对比。研究发现,合成产物通过硅烷基团的引入,改善了环氧丙烯酸酯的柔韧性。同时,由于硅烷偶联剂基团在固化过程中水解露出的硅羟基增强了对无机底材的附着力,使得紫外光固化胶粘剂的综合性能得到了优化和改善。     

NR/改性气相法白炭黑复合材料的性能研究

在改性气相法自炭黑填充NR胶料中加入粘合剂RH，研究粘合剂RH用量对胶料性能的影响，并与偶联剂Si69／气相法白炭黑胶料进行对比。结果表明，粘合剂RH的加入明显改善了硫化胶的物理性能，拉伸强度提高10％以上；粘合剂RH用量为4份时，硫化胶的综合物理性能最佳；有机改性剂M2改性气相法白炭黑参与了橡胶的共硫化，使硫化胶的交联密度增大；偶联剂Si69对硫化胶物理性能的改善效果不及粘合剂RH。     

甲基改性硅溶胶的制备与疏水性分析

通过溶胶-凝胶工艺,以甲基三甲氧基硅烷(MTMS)为基料对碱性硅溶胶进行改性,将改性后的硅溶胶涂覆在铝板表面,制备出具有低表面能、耐高温的含硅透明疏水涂层.考察了pH和热处理温度对涂层水接触角的影响,以傅里叶变换红外光谱仪对涂层进行了表征,用同步热分析仪对比研究硅溶胶和改性硅溶胶干燥后在空气中的热重-差热(TG-DTA...     

硅溶胶结合不定形耐火材料的研究及应用现状

总结了硅溶胶结合不定形耐火材料(包括浇注料、捣打料、喷射料和压入料)的性能研究和应用现状,并展望了硅溶胶结合耐火材料技术研究的方向和前景。     

二氧化硅粉体改性E—Si／CE固化动力学的研究

采用非等温差示扫描量热法（DSC）研究了纳米二氧化硅（SiO2）和微米SiO2的混合粉体改性环氧基硅烷（E—Si）／氰酸酯（CE）树脂体系固化动力学;用Kissinger、Crane和Ozawa法确定固化动力学参数。结果表明,Kissinger式求得的表观活化能为66．09kJ／mol;Ozawa法求得的表观活化能为7001kJ／mol;根据Crane理论计算该体系的固化反应级数为0.89。计算了不同升温速率所对应的不同温度的频率因子和反应速率常数;求得了改性体系的固化工艺参数：凝胶温度130．74℃、固化温度160．96℃和后处理温度199.16℃,确定了体系的最佳固化工艺。与E—Si／CE体系对比表明,SiO2的加入可以降低E—Si／CE体系的活化能,使其固化能在较低温度下进行。     

Synthesis and characterization of hybrid materials based on graphene oxide and silica nanoparticles and their effect on the corrosion protection properties of epoxy resin coatings

This study focuses on the use of tetraethyl orthosilicate (TEOS) as a silica source to decorate the surface of graphene oxide (GO) nanosheets and the use of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Z-6020) as a coupling agent through a one-step in-situ sol-gel process. The results of the Fourier transform infrared spectroscopy (FT-IR), UV-visible, X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) revealed that fine SiO₂ nanoparticles have successfully been synthesized on the basal plane of GO by covalent bonding. The dispersion of GO sheets and GO–SiO₂ nanohybrids within the epoxy matrix was studied using XRD and SEM techniques. Then, the effect of incorporating 0.1?wt% GO sheets and GO–SiO₂ nanohybrids on the corrosion protection and barrier performance of the epoxy coating was also investigated. The results showed that the incorporation of GO–SiO₂ into the epoxy matrix improved its thermal stability. The electrochemical impedance spectroscopy (EIS) test, potentiodynamic polarization and cathodic disbonding test showed that the corrosion protection performance was significantly enhanced by the incorporation of GO–SiO₂ hybrids into the epoxy resin compared to epoxy/GO and neat epoxy resin, respectively. The water contact angle (CA) results confirmed the reduction of the hydrophobic nature of the surface after the incorporation of GO–SiO₂ hybrids.     

Dispersion of phosphovanadates on silica gel chemically modified with silane coupling agents having an amino group and their catalytic activities for methanol oxidation

Phosphotetradecavanadate (PV14) was dispersed on a silica gel chemically modified with a silane coupling agent (AnPS-SiO₂) by an equilibrium adsorption method. The PV14 contents approximately correlated with the V(IV) spin contents by ESR. PV14 dispersed on AnPS-SiO₂ resulted in a quite high selectivity for formaldehyde such as 97% in methanol oxidation.     

Durable nanocomposite adhesives based on polyacrylates and surface-modified colloidal silica

Surface-modified colloidal silica (M-CS) nanoparticles were successfully synthesized from colloidal silica (CS) and methyltrimethoxysilane using sol–gel method and characterized by Fourier transform-infrared spectroscopy. Both CS and M-CS were then incorporated into acrylic adhesives. M-CS particles in 2-ethoxyethanol had similar particle size to pure CS based on the characterization by DLS. The morphologies of M-CS particles in acrylic adhesives examined by TEM showed more homogeneous dispersities than that of pure CS which were aggregated and phase separated in acrylic adhesives. In addition, the thermal properties of the nanocomposite acrylic adhesives determined by thermogravimetric analyses and differential scanning calorimetry showed higher glass transition temperature and thermal properties than pure acrylic adhesives. Finally, the 180° peel strength of nanocomposite acrylic adhesives was higher than pure adhesives with improved durabilities.     

Fabricating colloidal crystals and construction of ordered nanostructures

Colloidal crystals of polymeric or inorganic microspheres are of extensive interest due to their potential applications in such as sensing, optics, photonic bandgap and surface patterning. The article highlights a set of approaches developed in our group, which are efficient to prepare colloidal crystals with ordered voids, patterned colloidal crystals on non-planar surfaces, heterogeneous colloidal crystals of different building blocks, colloidal crystals composed of non-spherical polyhedrons, and colloidal crystals of non-close-packed colloidal microspheres in particular. The use of these colloidal crystals as templates for different microstructures range from nanoscale to micron-scale is also summarized.