Fabrication and characterization of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles and polyurethane/(TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>) nanocomposite films

TiO₂–SiO₂ composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO₂–SiO₂ composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO₂–SiO₂) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO₂–SiO₂ composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO₂–SiO₂ composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO₂–SiO₂ core surface via surface functionalized reaction. The particle size of TiO₂–SiO₂ composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO₂–SiO₂ composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO₂–SiO₂ composite nanoparticles are well dispersed in the PU matrix.     

Direct formation of SiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript> composite nanoparticles with high surface area and high thermal stability by sol–gel-hydrothermal process

SnO₂/SiO₂ composite nanoparticles were prepared by sol–gel-hydrothermal process and their physico-chemical structure and photocatalytic property were investigated. The results of XRD, TEM and FT-IR indicated that SnO₂ crystallites with the tetragonal rutile structure were well-developed directly during hydrothermal process. The SnO₂/SiO₂ composite nanoparticles owned narrow size distribution, large specific surface area, and good thermal stability. As the presence of 25.0 wt% SiO₂, the SnO₂ nanoparticles were about 4.0 nm in diameter and the specific surface area was 259.0 m²/g. After calcination at 800 °C, the crystalline grain size maintained 16.2 nm and the surface area still remained 132.6 m²/g. The SnO₂/SiO₂ composite nanoparticles showed better photocatalytic activity than pure SnO₂ nanoparticles.     

Synthesis and properties of silica/polystyrene/polyaniline conductive composite particles

In this study, silica/polystyrene/polyaniline (SiO₂/PS/PANI) conductive composite particles were synthesized by four sequential reactions. The nanosized SiO₂ particles were synthesized from tetraethoxysilane (TEOS) by a sol–gel process with water as the solvent medium, followed by a surface modification with triethoxyvinylsilane; then the surface modified SiO₂ particles were used as seeds to synthesize SiO₂/PS composite particles with soapless seeded emulsion polymerization. Finally, the SiO₂/PS particles were used as seeds to synthesize the SiO₂/PS/PANI conductive composite particles. The sol–gel process of SiO₂, the effect of surface modification, and several other factors that influenced polymerization of styrene in the soapless seeded emulsion polymerization will be discussed. Either potassium persulfate (KPS) or 2,2′‐azobis(isobutyramidine) dihydrochloride (AIBA) was used as the initiator to synthesize the uniform SiO₂/PS particles successfully, and the cross‐section morphology of the SiO₂/PS particles was found to be of a core–shell structure, with SiO₂ as the core, and PS as the shell. The SiO₂/PS particles were well dispersed in many organic solvents. In the following step to synthesize SiO₂/PS/PANI conductive composite particles, sodium dodecyl sulfate (SDS) played an important role, specifically, to absorb aniline onto the surfaces of the SiO₂/PS particles to carry out the polymerization of aniline over the entire surface of the particles. The conductivity of the SiO₂/PS/PANI composite particles approached that of semiconductive materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 342–354, 2005     

具有双亲特性的水相哑铃型SiO2纳米粒子的制备

以纳米SiO2水溶胶为原料,3?氨丙基三乙氧基硅烷(APTES)和3?氯丙基三乙氧基硅烷(CPTES)为改性剂,在水基环境下分别对SiO2纳米粒子进行改性,得到了具有亲水特性的APTES改性SiO2粒子和具有亲油特性的CPTES改性SiO2粒子水溶胶。2种粒子按不同比例混合,利用接枝在SiO2粒子表面氨基和氯丙基的取代反应,使得2种具有亲水/亲油特性的改性SiO2纳米粒子偶联,制备了粒径为40~50 nm的哑铃型SiO2纳米粒子。并通过透射电镜(TEM)、傅里叶变换红外光谱(FT?IR)、X射线光电子能谱(XPS)以及动态光散射(DLS)等方法对其进行了系统表征。结果表明,2种粒子成功偶联形成了具有哑铃型结构的水相SiO2纳米粒子,该粒子两面具有不同的亲水性,粒径近似等于APTES改性SiO2粒子和CPTES改性SiO2粒子的粒径之和。     

Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO₃/SiO₂ three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO₃/SiO₂ two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO₃ was encapsulated by the obtained SiO₂. After being modified by silane coupling agent, the CaCO₃/SiO₂ composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO₃/SiO₂ three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO₃/SiO₂ two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO₃/SiO₂ composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.     

Preparation of Cu/SiO2 Catalyst by Solution Exchange of Wet Silica Gel

Structural formation process of Ni/SiO₂ and Cu/SiO₂ catalysts prepared by solution exchange of wet silica gel was investigated. Microstructures of Cu/SiO₂ and Ni/SiO₂ were quite different from each other. In the case of Cu/SiO₂, Cu particles with diameter of ca. 3–5 nm dispersed homogeneously at less Cu content, and the particle size of Cu as well as pore size of silica gel support increased with increasing Cu content. In the Ni/SiO₂, the Ni particles with diameter of ca. 6–10 nm gathered densely to form aggregates in silica matrix resulting in sea-island structure, whereas the size of Ni particle slightly increased with increasing Ni content. The difference in the structure of the metal-silica composites is probably caused by the difference in interaction between silica gel network and metal ions during drying and heating processes.     

Synthesis and Polymerization Kinetics of Polystyrene Grafting using Azo-groups Bounded SiO2 as an Initiator

This work presents a new method for synthesis of inorganic/organic hybrid nanoparticles via the in-situ polymerization by the use of the azo-groups bounded silica nanoparticles as a radical initiator and styrene as a model vinyl-monomer. The synthesis and the structure of silica/polystyrene (SiO₂/PS), and the polymerization kinetics of the styrene initiated by the azo-groups bounded SiO₂ nanoparticles are studied with techniques such as FTIR, XPS, DSC, GPC, and TEM. Results show that the SiO₂-g-PS nanoparticles are synthesized successfully, and the resulting hybrid nanoparticles have a core-shell structure with SiO₂ in the core and the polystyrene on the outside layer. The percentage of the grafted PS on the SiO₂ surface increases with the progress of the polymerization before 6 h, and the largest amount of the grafted PS reaches 33% of the silica nanoparticles.

Consequently, the size of the nanoparticles increases ca. 20 nm upon the polystyrene grafting. The molecular weight of the grafted PS increases with the polymerization, and it has reached a much large value in the first several polymerization hours while it keeps a constant value approximately in the following polymerization process. Meanwhile, the polydispersity index of the grafted PS gradually increases with the progress of the polymerization. These phenomena agree with the theory of the traditional free radical polymerization very well.     

Synthesis of silica-polystyrene core-shell nanoparticles via surface thiol-lactam initiated radical polymerization

This paper reports the synthesis of structurally well-defined silica-polystyrene (SiO₂@PS) hybrid nanoparticles using a thiol-lactam-initiated, radical-polymerization technique. The surface of silica particles, 80 nm in size, were functionalized with (3-mercaptopropyl) trimethoxysilane and used as seeds in the polymerization of styrene in the presence of butyrolactam. ¹H nuclear magnetic resonance and X-ray photoelectron spectroscopy showed that the thiol groups on the SiO₂ surface could initiate polymerization with the aid of butyrolactam. Transmission electron microscopy showed that the hybrid particles had uniform core-shell morphologies. The molecular weight of grafted PS increased with increasing polymerization time.     

玻璃微珠/Ag/TiO2可见光催化剂的制备与表征

通过离子交换法将Ag纳米颗粒负载于玻璃微珠的表面及浅表层,并以钛酸四丁酯的乙醇溶液为前驱体,将TiO₂负载于包含银的玻璃微珠表面,制得一种玻璃微珠/Ag/TiO₂复合光催化剂。由于纳米银的表面等离子体吸收效应,该复合光催化剂具有一定的可见光响应特性。利用XRD、SEM对样品进行表征,可发现玻璃微珠表面形成一层均匀多孔的锐钛矿TiO₂,其粒径均在50 nm左右。由漫反射光谱可得出该催化剂具有较强的可见光吸收,并在降解甲基橙溶液的试验中表现出较好的可见光催化活性。     

Synthesis of Fe3O4\SiO2\Ag nanoparticles and its application in surface-enhanced Raman scattering

To obtain a recyclable surface-enhanced Raman scattering (SERS) material, we developed a composite of Fe₃O₄\SiO₂\Ag with core\shell\particles structure. The designed particles were synthesized via an ultrasonic route. The Raman scattering signal of Fe₃O₄ could be shielded by increasing the thickness of the SiO₂ layer to 60 nm. Dye rhodamine B (RB) was chosen as probe molecule to test the SERS effect of the synthesized Fe₃O₄\SiO₂\Ag particles. On the synthesized Fe₃O₄\SiO₂\Ag particles, the characteristic Raman bands of RB could be observed when the RB solution was diluted to 5 ppm (1×10⁻⁵ M). Furthermore, the synthesized particles could keep their efficiency till four cycles.     

Preparation of poly(methyl methacrylate)/CaCO3/SiO2 composite particles via emulsion polymerization

A novel method to prepare organic/inorganic composite particles, i.e. poly(methyl methacrylate)/CaCO₃/SiO₂ three-component composite particles, using emulsion polymerization of methyl methacrylate with sodium lauryl sulfate as a surfactant in an aqueous medium was reported. CaCO₃/SiO₂ two-component inorganic composite particles were obtained firstly by the reaction between Na₂CO₃ and CaCl₂ in porous silica (submicrometer size) aqueous sol and the specific surface area of the particles was measured by the Brunauer–Emmett–Teller (BET) method. The results show that the BET specific surface area of the CaCO₃/SiO₂ composite particle is much smaller than that of the silica particle, indicating that CaCO₃ particles were adsorbed by porous silica and that two-component inorganic composite particles were formed. Before copolymerization with methyl methacrylate, the inorganic composite particles were coated with a modifying agent through covalent attachment. The chemical structures of the poly(methyl methacrylate)/CaCO₃/SiO₂ composite particles obtained were characterized by Fourier transform IR spectroscopy and thermogravimetric analysis. The results show that the surface of the modified inorganic particles is grafted by the methyl methacrylate molecules and that the grafting percentage is about 15.2%.     

Solid-phase photocatalytic degradation of polystyrene plastic with TiO2 as photocatalyst

Solid-phase photocatalytic degradation of polystyrene (PS) plastic with TiO₂ as photocatalyst was investigated in the ambient air under ultraviolet light irradiation. Higher weight loss rate, lower average molecular weight, increased carbonyl peak intensity, less volatile organics and more CO₂ emitted with irradiation in PS-TiO₂ composite sample compared to pure PS sample were observed. These facts indicated the higher photodegradation rate of PS-TiO₂ sample than that of PS sample, and emphasized the potential of the composite sample in bring about complete photodegradation of polystyrene plastic. It is implied that the degradation initially occurred over TiO₂ particles, followed by the diffusion reaction with the aid of reactive oxygen species generated on TiO₂ particle surface.     

Preparation and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>composite particles

Using Fe₃O₄ nano-particles as seeds, a new type of Fe₃O₄/Au composite particles with core/shell structure and diameter of about 170 nm was prepared by reduction of Au³⁺ with hydroxylamine in an aqueous solution. Particle size analyzer and transmission electron microscope were used to analyze the size distribution and microstructure of the particles in different conditions. The result showed that the magnetically responsive property and suspension stability of Fe₃O₄ seeds as well as reduction conditions of Au³⁺to Au⁰are the main factors which are crucial for obtaining a colloid of the Fe₃O₄/Au composite particles with uniform particle dispersion, excellent stability, homogeneity in particle sizes, and effective response to an external magnet in aqueous suspension solutions. UV-Vis analysis revealed that there is a characteristic peak of Fe₃O₄/Au fluid. For particles with d(0.5)=168 nm, the λmax is 625 nm.     

A facile two-step modifying process for preparation of poly(SStNa)-grafted Fe3O4/SiO2 particles

This article reports the synthesis of the poly(sodium 4-styrenesulfonate)-grafted Fe₃O₄/SiO₂ particles via two steps. The first step involved magnetite nanoparticles (Fe₃O₄) homogeneously incorporated into silica spheres using the modified Stöber method. Second, the modified silica-coated Fe₃O₄ nanoparticles were covered with the outer shell of anionic polyelectrolyte by surface-initiated atom transfer radical polymerization. The resulted composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive microscopy (EDS), Fourier transform-infrared (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and vibration sample magnetometer (VSM). The XRD results indicated that the surface modified Fe₃O₄ nanoparticles did not lead to phase change compared with the pure Fe₃O₄. TEM studies revealed nanoparticles remained monodisperse. The detection of sulfur and sodium signals was a convincing evidence that sodium 4-styrenesulfonate was grafted onto the surface of the magnetic silica in XPS analysis. Finally, super-paramagnetic properties of the composite particles, and the ease of modifying the surfaces may make the composites of important use in mild separation, enzyme immobilization, etc.     

Pickering emulsion polymerization kinetics of styrene: Comparison of bare and surface modified SiO2 nanoparticles

A step towards the understanding of some mechanistic events occurring in the styrene Pickering emulsions, using a SiO₂ dispersion, is presented. Polymerizations at 80°C with different levels of a water soluble initiator were performed. The emulsion polymer content was ca. 15% with conversions close to 90%. With conversion and particle size measurements, the particle density was estimated for bare and surface modified SiO₂ particles. Then, the average number of radicals per particle was inferred, yielding a pseudo-bulk type polymerization. It was found that bare SiO₂ nanoparticles do not participate in the nucleation mechanism; however, they, along with the initiator, promote an enhanced oligomer coagulation. On the other hand, the hexadecyltrimethylammonium bromide modified SiO₂ nanoparticles do participate in the nucleation and coagulation mechanisms, yielding more stable and smaller poorly-covered polymer particles. This approach allowed untangling some events such as: particle nucleation, radical entry to particles, particle density, coagulation and vitreous and Trommsdorff effects.     

Characterization and application of Fe3O4/SiO2 nanocomposites

A sol-gel procedure was used to cover Fe₃O₄ nanoparticles with SiO₂ shell, forming a core/shell structure. The core/shell nanocomposites were synthesized by a two-step process. First, Fe₃O₄ nanoparticles were obtained through co-precipitation and dispersed in aqueous solution through electrostatic interactions in the presence of tetramethylammonium hydroxide (TMAOH). In the second step, Fe₃O₄ was capped with SiO₂ generated from the hydrolyzation of tetraethyl orthosilicate (TEOS). The structure and properties of the formed Fe₃O₄/SiO₂ nanocomposites were characterized and the results indicate that the Fe₃O₄/SiO₂ nanocomposites are superparamagnetic and are about 30 nm in size. Bioconjugation to IgG was also studied. Finally, the mechanism of depositing SiO₂ on magnetic nanoparticles was discussed.     

Syntheses of MO2 (M=Si, Ce, Sn) nanoparticles by solid-state reactions at ambient temperature

Nano oxides (SiO₂, CeO₂, SnO₂) were successfully synthesized by solid-state reactions at ambient temperature. The nanoparticles were characterized by X-ray powder diffraction, TEM, BET, and TGA-DTA. The SiO₂ particles were also investigated using IR spectra. Effects of calcination on the nanoparticles were studied in this paper. The solid-state reaction technique is a convenient, inexpensive and an effective preparation method of monodisperse oxide nanoparticles in high yield. The mechanisms of the formation of nano materials by solid-state reactions at ambient temperature were primarily investigated.     

SiO2/ZnO复合纳米粒子的制备及表征

采用双注控制沉积法(Controlled Double-Jet Precipitation,CDJP)将反应物添加到含有SiO₂的溶液中,通过直接的表面反应来制备单分散的SiO₂/ZnO复合纳米粒子,并对其进行了表征。透射电镜(TEM)观察表明,SiO₂表面有一层ZnO纳米颗粒或薄层。对复合纳米粒子SiO₂/ZnO进行X射线衍射(XRD)分析,复合颗粒的衍射峰与单独的氧化锌的衍射峰完全一致。能量弥散X射线法(EDX)分析表明,复合颗粒中含有Zn、Si、O元素。荧光光谱表明有ZnO的吸收峰。     

PREPARATION OF POLYSTYRENE/SiO2 COMPOSITE NANOPARTICLES BEARING SULFONIC GROUPS ON THE SURFACE VIA EMULSION COPOLYMERIZATION USING A POLYMERIZABLE EMULSIFIER

Functionalized PS/SiO_2 composite nanoparticles bearing sulfonic groups on the surface were successfully synthesized via emulsion copolymerization using a polymerizable emulsifierαolefin solfonate(AOS).As demonstrated by transmission electron microscopy and atomic force microscopy,well-defined core-shell PS/SiO_2 composite nanoparticles with a diameter of 50 nm were obtained.Sulfonic groups introduced onto the surface of the composite nanoparticles were quantified by FTIR,and can be controlled to some ex...     

The release of TiO2 and SiO2 nanoparticles from nanocomposites

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO₂ or amorphous SiO₂ nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO₂ and TiO₂ nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.