Hybrid titanium dioxide/PS-b-PEO block copolymer nanocomposites based on sol-gel synthesis

The poly(styrene)-b-poly(ethylene oxide) (SEO) amphiphilic block copolymer, with two different molecular weights, has been used as a structure directing agent for generating nanocomposites of TiO(2)/SEO via the sol-gel process. SEO amphiphilic block copolymers are designed with a hydrophilic PEO-block which can interact with inorganic molecules, as well as a hydrophobic PS-block which builds the matrix. The addition of different amounts of sol-gel provokes strong variations in the self-assembled morphology of TiO(2)/SEO nanocomposites with respect to the neat block copolymer. As confirmed by atomic force microscopy (AFM), TiO(2)/PEO-block micelles get closer, forming well-ordered spherical domains, in which TiO(2) nanoparticles constitute the core surrounded by a corona of PEO-blocks. Moreover, for 20?vol% sol-gel the generated morphology changes to a hexagonally ordered structure for both block copolymers. The cylindrical structure of these nanocomposites has been confirmed by the two-dimensional Fourier transform power spectrum of the corresponding AFM height images. Affinity between titanium dioxide precursor and PEO-block of SEO allows us to generate hybrid inorganic/organic nanocomposites, which retain the optical properties of TiO(2), as evaluated by UV-vis spectroscopy.     

Micropatterning of Ag and Au nanoparticles by microcontact printing and block copolymer micelles

Micropatterns of gold and silver nanoparticles were successfully obtained by combining microcontact printing and poly(2-vinylpyridine)-block-poly(cyclohexyl metharylate) (P2VP-b-PCHMA) diblock copolymer micelles with metal precursors. The metal ions were incorporated into poly(2-vinylpyridine) blocks and located into the core area of micelles. Then the metal-loaded micellar solutions were used as inks which were spin coated as thin layers onto polydimethylsiloxane stamps and transferred onto the substrates by stamping. Different morphologies of micellar aggregates were formed on the substrates depending on the stamp morphologies, and single layers of nanoparticles in the micropattern were obtained by the reducing process.     

嵌段硅橡胶及其感压导电纳米复合材料研究

以LiOH为引发荆、DMF为促进剂,D4、P4、V4为单体,采用阴离子开环聚合方法,合成了特定分子结构的高分子量三元嵌段共聚硅橡胶;应用凝胶色谱法、红外光谱及核磁氢谱等方法对合成产物进行了表征;介绍了特导电纳米炭/嵌段硅橡胶感压导电复合材料的制备技术与性能.     

Synthesis of Ag2S and Ag2Se nanoparticles in self assembled block copolymer micelles and nano-arrays fabrication

This paper describes a simple approach based on self assembled polystyrene-block-poly(4-vinylpyridine) (PS-P4VP) copolymer micelles for the fabrication of ordered 2-dimesional nano-arrays of Ag₂S and Ag₂Se. The nanoparticles were synthesized directly inside the P4VP micelles core at room temperature and nano-arrays were obtained by spin coating on silicon wafer. High resolution-transmission electron microscopy and powder X-ray diffraction characterization suggests the nanoparticles are crystalline. Higher band gap energy (1.76 eV for Ag₂S and 1.35 eV for Ag₂Se) compared to their bulk materials obtained from the absorption studies reveals that the nanoparticles are within the quantum confinement regime.     

Preparation of silver nanocomposites stabilized by an amphiphilic block copolymer under ultrasonic irradiation

Silver nanoparticles were synthesized by using amphiphilic block copolymer Polyacrylonitrile-block-poly(ethylene glycol)-blcok-Polyacrylonitrile (PAN-b-PEG-b-PAN, PEA) based on the flexibility of the copolymer chains and the complex effect of –CN in the polyacrylonitrile with Ag⁺ ion and Ag under ultrasonic irradiation. The product was characterized by X-ray Diffraction (XRD), Fourier Transfer Infrared Spectrometer (FTIR), Transmission Electron Microscope (TEM), UV–Vis spectrum and Thermal Gravity Analysis (TGA). The results revealed that the size and size distribution of the resulting silver nanoparticles prepared basing on the copolymer were strongly dependent on the initial concentration of the silver ion solution and the irradiation conditions. Low initial silver ion concentration allowed for yielding silver nanoparticles with a small size and the size of the silver nanoparticles increased with increasing of silver ion concentration. The silver crystal was polycrystalline with a cubic structure, as confirmed by XRD. This work provides a simple route for the in situ synthesis of Ag nanoparticles.     

Fabrication and characterization of Ag/calcium silicate core-shell nanocomposites

The Ag/calcium silicate nanocomposite with core-shell nanostructure has been successfully synthesized using Ag solution, Ca(NO₃)₂·4H₂O and Na₂SiO₃·9H₂O in ethanol/water mixed solvents at room temperature for 48 h. Ag solution was previously prepared by microwave-assisted method in ethylene glycol (EG) at 150 °C for 10 min. The nanocomposites consisted of Ag core and an amorphous calcium silicate shell. The XRD and EDS results confirmed that the product was the Ag/calcium silicate nanocomposite. The TEM micrographs indicated that the Ag/calcium silicate nanocomposite was core-shell nanoparticles. The effects of Ca(NO₃)₂·4H₂O and Na₂SiO₃·9H₂O concentration on the shells of Ag/calcium silicate nanocomposite were investigated. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectra (EDS). This method is simple, fast and may be extended to the synthesis of the other kinds of core-shell nanocomposites.     

Ag／Si3N4纳米复合材料的电学性质研究

利用干压方法制得了０－７０ｖｏｌ％Ａｇ弥散的Ａｇ／Ｓｉ３Ｎ４纳米复合材料。借助于ＳＥＭ，ＥＤＳ和复阻抗谱等方法研究了Ａｇ／Ｓｉ３Ｎ４复合材料的结构和反常电学性质。结果表明，纳米Ａｇ粒子以μｍ尺寸的团聚体形式存在于纳米Ｓｉ３Ｎ４基体中。     

Swelling properties and bioactivity of silica gel/pHEMA nanocomposites

A novel hydrogel based on 2-hydroxyethyl- methacrilate and SiO₂ nanoparticles was prepared. The filler was added at a concentration of 30% w/w of silica nanoparticles to the mass of polymer. The composite material was characterised as far as concerns swelling behaviour in comparison to pHEMA. Swelling ratio of modified pHEMA was higher. Bioactivity of both SiO₂ nanoparticles and the modified hydrogel was evaluated by soaking samples into a simulated body fluid (SBF). FT-IR spectroscopy, scanning electron microscopy (SEM) and energy dispersive system (EDS) results suggest silica nanoparticles keep bioactive in the polymer. SiO₂ filler in a p(HEMA) matrix makes the composite bioactive. Therefore, these composites can be used to make bioactive scaffold for bone engineering.     

Nanostructured systems based on SBS epoxidized triblock copolymers and well-dispersed alumina/epoxy matrix composites

In the present research, the effect of addition of (1 wt.% and 3 wt.%) alumina nanoparticles (Al₂O₃) to epoxy modified by poly(styrene-b-butadiene-b-styrene) (SBS) epoxidized triblock copolymer was studied. The microstructure of final hybrid composites was studied with atomic force microscopy (AFM). Composites showed homogeneously dispersed Al₂O₃ nanoparticles in the epoxy matrix containing polystyrene (PS) microphase separated nanodomains. Dynamic mechanical analyses (DMA), flexural and fracture toughness investigations were carried out. The glass transition temperature of epoxy matrix has been retained unchanged by the addition of Al₂O₃ nanoparticles. The nanostructured epoxy systems based on SBS epoxidized triblock copolymer and well-dispersed Al₂O₃ nanoparticles allowed an increase in fracture toughness maintaining the transparency and stiffness of neat epoxy.     

Block copolymer templated synthesis of mesoporous WO3/carbon nanocomposites

Journal of Materials Science - We synthesize mesoporous WO3/carbon composites with PS-PVP-PEO polymeric template. The molecularly dissolved polymer in THF self-assembles in positively charged...     

Synthesis,characterization, and dispersion behavior of ZnO/Ag nanocomposites

ZnO/Ag nanocomposites that are composed of quasi-spherical nanoparticles with diameters of several nanometers have been successfully generated by a two-step liquid precipitation method. The as-prepared ZnO/Ag nanocomposites were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). The dispersion behaviors of the ZnO/Ag nanocomposites in isopropanol with using nonionic dispersants such as stearic acid, PVP K17, and PVP K30 were investigated by conventional sedimentation method, dynamic light scattering method (DLS) and TEM observation. Both the PVP K17 and PVP K30 could disperse the ZnO/Ag nanoparticles effectively in isopropanol. It is proposed that the nonionic dispersants could form absorbed PVP molecule layers on the surfaces of the ZnO/Ag nanoparticles, prohibiting their agglomeration and enhancing their dispersion stability in isopropanol. This work is helpful for further investigating the potential applications of ZnO/Ag nanocomposites in the fields of medical plastics and sterilization.     

Shape transformation and relaxation dynamics of photoexcited TiO2/Ag nanocomposites

The laser-induced sintering of TiO2 nanoparticles into larger nanospheres is accelerated by adsorbed silver particles. For the same weight fraction of silver, silver nanoparticles of 5 nm in diameter modify TiO2 nanoparticles more effectively than those of 1.5 nm do, suggesting that the photocatalysis of TiO2 nanoparticles as well as their stability is highly dependent on the sizes, the shapes, and the distribution of adsorbed metal nanoparticles. The photoexcited electrons of TiO2 nanoparticles are quenched at trap sites and surface states by transfer to the conduction band of silver, implying that the presence of adsorbed silver nanoparticles enhances the photocatalytic effect of TiO2.     

Nanostructured Ag platforms as biosensors of nucleobase chains

Nanostructured Ag platforms have been obtained by simple chemical procedure and characterized by AFM (atomic force microscopy) measurements, for use in biosensing by means of SERS (surface-enhanced Raman scattering) spectroscopy. The SERS efficiency of these substrates has been verified by microRaman measurements on small RNA chains with different nucleobase content, showing sensitivity near attomole level. It is our opinion that these metal substrates may be widely used as appropriate sensors for detecting biomolecules in many applications concerning medical diagnostics, pharmacological research and nanomaterials technology.     

Morphologies of block copolymer melts

Morphology formation by block copolymers in the melt is reviewed, considering both theoretical and experimental aspects. Comprehensive tables provide information on morphology identification for many block copolymer systems. A particular focus is on recent structural studies on ABC triblocks and rod–coil copolymers.     

Synthesis and electrocatalytic activity of multi-walled carbon nanotubes/Cu–Ag nanocomposites

Cu–Ag bimetallic nanoparticles with atomic ratio of 2.1:1 and diameter in the range of 15–30 nm were decorated on acid-treated multi-walled carbon nanotubes by a chemical reduction method, which was characterized by transmission electron microscope (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). The Cu–Ag/MWNTs nanocomposites were used to construct a modified electrode toward biosensing of H₂O₂ with a high sensitivity. The catalytic ability of MWNTs/Cu–Ag toward H₂O₂ was much better than that of MWNTs/Cu and MWNTs/Ag, which indicated that there is a cooperation effect between Cu and Ag.     

Synthesis and characterization of Ag/polypyrrole nanocomposites based on silver nanoparticles colloid

Ag/polypyrrole nanocomposites were successfully synthesized via in situ chemical oxidation polymerization of pyrrole based on mercaptocarboxylic acid capped Ag nanoparticles colloid. Scanning electron microscopy (SEM) measurement showed that the obtained Ag/polypyrrole nanocomposites were spherical. Transmission electron microscopy (TEM) measurement showed that the Ag nanoparticles were inside the polypyrrole particles and had a little aggregation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectra were used to characterize the structure of the obtained Ag/polypyrrole nanocomposites. A possible formation mechanism of the Ag/polyrrole nanocomposites was also proposed.     

纳米ZnO/Ag的制备及其光催化性能

以Zn(CH3COO)2·2H2O和AgNO3为原料,丙烯酰胺为单体,N,N′-亚甲基双丙烯酰胺为交联剂,用高分子凝胶法在较低的温度下制备出纳米ZnO/Ag.对纳米ZnO/Ag的结构和性能进行了表征,并研究了它的光催化活性.结果表明:在这个方法中,利用丙烯酰胺自由基聚合反应,同时利用网络剂有两个活化双健的双功能团效应,将高分子链联结起来构成网络.高分子凝胶形成的极小且均匀的网络限制了ZnO/Ag晶粒之间的团聚.制备出的纳米ZnO/Ag粉料颗粒为球形,未被Ag包覆的纳米ZnO的平均粒径约15 nm,被Ag包覆的纳米ZnO的平均粒径约45 nm.在次甲基蓝水溶液中加入3 g/LZnO/Ag粉料后,次甲基蓝的降解率为100%.沉积贵金属Ag使ZnO纳米粉料的光催化活性得到了很大提高,且可以重复使用.     

Morphology and crack toughness behaviour of nanostructured block copolymer/homopolymer blends

The crack initiation and propagation behaviour of styrene-butadiene (SB) star block copolymer/polystyrene blends (ST3/PS) forming PS-rich and polybutadiene (PB)-rich nanosized domains by self-assembling have been investigated using the essential-work-of-fracture (EWF) approach. Three morphological transitions have been observed, which are crucial to understand the crack toughness behaviour: (i) 0-30 wt.% PS homopolymer: A co-continuous domain structure of PS-rich and PB-rich domains has been observed. For PS homopolymer fraction (?_PS) < 10 wt.% PS homopolymer (i.e. only pure ST3) the rubbery PB-rich phase forms the major phase and for ?_PS > 10 wt.% the glassy PS-rich phase. (ii) At 40-60 wt.% PS homopolymer, a layer-like morphology is formed where the PS-rich layer thickness is ?50 nm, a critical dimension, which is crucial for understanding the ductile-to-semiductile transition. (iii) For 80 wt.% PS homopolymer, PS-rich phase starts to form the matrix combined with a transition from shear stress dominated (shear yielding) to normal stress dominated behaviour (PS-like crazes). The co-continuous morphology at 20 wt.% and 30 wt.% PS is capable of improving toughness of block copolymers, demonstrated by the observed maximum in the non-essential work of fracture and thus explaining a new way of toughening of polymers while retaining high transparency. The correspondence between the ductile-to-semiductile transition and the change in the shape of plastic zone from circular to elliptical as revealed from strain field analysis could be clearly reaffirmed by the observed transition from shear to normal force induced deformation in the fractured surface analysis of these blends. The conceptual correspondence of βw_p and w_e with T_J and δ_0.2 respectively reveal that resistance against crack propagation (βw_p and T_J) is morphology sensitive while the resistance against crack initiation (w_e and δ_0.2) is matrix sensitive.