Superhydrophobic fabrics from hybrid silica sol-gel coatings: Structural effect of precursors on wettability and washing durability

Particle-containing silica sol was synthesized by co-hydrolysis and co-condensation of two silane precursors, tetraethylorthosilicate (TEOS) and an organic silane composed of a non-hydrolyzable functional group (e.g., alkyl, flourinated alkyl, and phenyl), and used to produce superhydrophobic coatings on fabrics. it has been revealed that the non-hydrolyzable functional groups in the organic silanes have a considerable influence on the fabric surface wettability. When the functional group was long chain alkyl (C16), phenyl, or flourinated alkyl (C8), the treated surfaces were highly superhydrophobic with a water contact angle (CA) greater than 170°, and the CA value was little affected by the fabric type. The washing durability of the superhydrophobic coating was improved by introducing the third silane containg epoxide group, 3-glycidoxypropyltrimethoxsilane (GPTMS), for synthesis. Although the presence of epoxide groups in the coating slightly reduced the fabrics' superhydrophobicity, the washing durability was considerably improved when polyester and cotton fabrics were used as substrates.

Photochromic fabrics from hybrid silica surface coatings

In this study, hybrid silica prepared by a sol-gel technique and doped with a photochromic dye was used to produce photochromic coatings on fabric surfaces. The coated fabrics showed a strong photochromic effect with very fast optical response speed. Good coating adhesion was obtained on wool fabrics. The photostability of the photochromic fabrics was improved by three different processes: adding a photo stabilizer, adjusting the surface wettability and sealing off the dye-containing pores with additional silica coating. Four UV stabilizers were added separately to the photochromic silica coatings to investigate their influence on the photostability and photochromic behaviour. The addition of UV stabilizers retarded the photochromic response and reduced photochromic absorption, but increased photochromic lifetime. Among the four UV stabilizers studied, the quencher resulted in the best improvement to the photostability with minimal reduction in the photochromic absorption. Increasing the hydrophobicity of the coating, and sealing-off the dye-containing pores were also found to improve photostability.

Functionalized mesoporous silica nanoparticles with redox-responsive short-chain gatekeepers for agrochemical delivery.

The controlled release of salicylic acid (SA), a key phytohormone, was mediated by using a novel decanethiol gatekeeper system grafted onto mesoporous silica nanoparticles (MSNs). The decanethiol was conjugated only to the external surfaces of the MSNs through glutathione (GSH)-cleavable disulfide linkages and the introduction of a process to assemble gatekeepers only on the outer surface so that the mesopore area can be maintained for high cargo loading. Raman and nitrogen sorption isotherm analyses confirmed the successful linkage of decanethiol to the surface of MSNs. The in vitro release of SA from decanethiol gated MSNs indicated that the release rate of SA in an environment with a certain amount of GSH was significantly higher than that without GSH. More importantly, in planta experiments showed the release of SA from decanethiol gated MSNs by GSH induced sustained expression of the plant defense gene PR-1 up to 7 days after introduction, while free SA caused an early peak in PR-1 expression which steadily decreased after 3 days. This study demonstrates the redox-responsive release of a phytohormone in vitro and also indicates the potential use of MSNs in planta as a controlled agrochemical delivery system.

Functionalized mesoporous silica nanoparticles for smart agrochemical delivery system

The agrochemical delivery system has been built up based on mesoporous silica nanoparticles as carriers in a controllable fashion. Several peer reviewed papers have been published with this research work. This delivery system will benefit for the future agricultural application.

Luminescence of Eu(III) beta-diketone complex supported on functionalized macroporous silica matrix

This work reports on the photoluminescent properties of the complex diequatris(thenoyltrifluoroacetonate) europium(III), which was adsorbed or supported on tubes of modified surface silica matrix. The luminescence data and the experimental intensity parameter results evidence the existence of high interactions between the complex [Eu(tta)(3)(H2O)(2)] and the modified surface matrix. The anchored complex on macroporous silica shows higher intensity parameter values suggesting that the Eu-0 bond becomes more covalent than the adsorbed one. Therefore, the hypersensitive character of the D-5(0) --> F-7(2) transition increases evidencing a high contribution of the dynamic coupling mechanism possibly due to highly polarizable chemical environments occupied by europium(III) ion. The lifetimes of the complex on silica matrices were measured. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Study of Hybrid Silica-Polyethyleneglycol Xerogels by Eu3+ Luminescence Spectroscopy

Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.

Multiscale Characterization of Acrylic Bone Cement Modified with Functionalized Mesoporous Silica Nanoparticles

Acrylic bone cement is widely used to anchor orthopedic implants to bone and mechanical failure of the cement mantle surrounding an implant can contribute to aseptic loosening. In an effort to enhance the mechanical properties of bone cement, a variety of nanoparticles and fibers can be incorporated into the cement matrix. Mesoporous silica nanoparticles (MSNs) are a class of particles that display high potential for use as reinforcement within bone cement. Therefore, the purpose of this study was to quantify the impact of modifying an acrylic cement with various low-loadings of mesoporous silica. Three types of MSNs (one plain variety and two modified with functional groups) at two loading ratios (0.1 and 0.2 wt/wt) were incorporated into a commercially available bone cement. The mechanical properties were characterized using four-point bending, microindentation and nanoindentation (static, stress relaxation, and creep) while material properties were assessed through dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, FTIR spectroscopy, and scanning electron microscopy. Four-point flexural testing and nanoindentation revealed minimal impact on the properties of the cements, except for several changes in the nano-level static mechanical properties. Conversely, microindentation testing demonstrated that the addition of MSNs significantly increased the microhardness. The stress relaxation and creep properties of the cements measured with nanoindentation displayed no effect resulting from the addition of MSNs. The measured material properties were consistent among all cements. Analysis of scanning electron micrographs images revealed that surface functionalization enhanced particle dispersion within the cement matrix and resulted in fewer particle agglomerates. These results suggest that the loading ratios of mesoporous silica used in this study were not an effective reinforcement material. Future work should be conducted to determine the impact of higher MSN loading ratios and alternative functional groups. (C) 2014 Elsevier Ltd. All rights reserved.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Magnetic Mesoporous Silica Spheres for Drug Targeting and Controlled Release

Magnetically functionalized mesoporous silica spheres with different size (average diameter, A.D.) from 150 nm to 2 mu m and pore size distribution were synthesized by generating magnetic FexOy nanoparticles onto the mesoporous silica hosts using the sol-gel method. The X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), N-2 adsorption/desorption results show that these composites conserved regular sphere morphology and ordered mesoporous structure after the formation of FexOy nanoparticles. XRD and X-ray photoelectron spectroscopy (XPS) analysis confirmed that the FexOy generated in these mesoporous silica hosts is mainly composed of gamma-Fe2O3. Magnetic measurements reveal that these composites with different gamma-Fe2O3 loading amounts possess super-paramagnetic properties at 300 K, and the saturation magnetization increases with increasing Fe ratio loaded.

Synthesis and luminescent properties of europium (III) schiff base complexes covalently bonded to silica xerogels

A new kind of luminescent organic-inorganic hydrid material consisting of Eu(III)-schiff base complex covalently bonded to silica xerogel was synthesized via the sol-gel method using a Eu (N-propylene salicylimine ligand) complex modified with pendant triethoxysilane groups (Eu(III)(salenHSi)). The Eu(III)(salenHSi) complex is characterized by Fourier transform infrared (FT-IR) spectroscopy. Luminescent properties of the complex and the resulted hybrid silica xerogels have been investigated at room temperature.

Patterning and optical properties rhodamine B-doped organic-inorganic silica films fabricated by sol-gel soft lithography

Rhodamine B (RB)-doped organic-inorganic silica films and their patterning were fabricated by a sol-gel process combined with a soft lithography. The resulted film samples were characterized by atomic force microscope (AFM), optical microscope and UV/Vis absorption and photoluminescence excitation and emission spectra. The effects of the concentration of the RB dye and heat treatment temperature on the optical properties of the hybrid silica films have been studied. Four kinds of patterning structures with film line widths of 5, 10, 20 and 50 mum have been obtained by micromolding in capillaries by a soft lithography technique. The RB-doped hybrid silica films present a red color, with an excitation and emission bands around 564 and 585 mum, respectively. With increasing the RB concentration, the emission intensity of the RB-doped hybrid silica films increases and the emission maximum presents a red shift. The emission intensity of the films decreases with increasing the heat treatment temperatures.

Carbon nanotube-reinforced siloxane-PMMA hybrid coatings with high corrosion resistance

Siloxane-polymethyl methacrylate hybrid films containing functionalized multiwall carbon nanotubes (CNTs) were deposited by dip-coating on carbon steel substrates from a sol prepared by radical polymerization of methyl methacrylate and 3-methacryloxy propyl-trimethoxysilane, followed by hydrolytic co-polycondensation of tetraethoxysilane. The correlation between the structural properties and corrosion protection efficiency was studied as a function of the molar ratio of nanotubes carbon to silicon, varied in the range between 0.1% and 5%. 29Si nuclear magnetic resonance and thermogravimetric measurements have shown that hybrids containing carbon nanotubes have a similar degree of polycondensation and thermal stability as the undoped matrix and exhibit and excellent adhesion to the substrate. Microscopy and X-ray photoelectron spectroscopy results revealed a very good dispersion of carbon nanotubes in the hybrid matrix and the presence of carboxylic groups allowing covalent bonding with the end-siloxane nodes. Potentiodynamic polarization curves and electrochemical impedance spectroscopy results demonstrate that CNTs containing coatings maintain the excellent corrosion protection efficiency of the hybrids, showing even a superior performance in acidic solution. The nanocomposite structure acts as efficient corrosion barrier, increasing the total impedance by 4 orders of magnitude and reducing the current densities by more than 3 orders of magnitude, compared to the bare steel electrode. © 2013 Elsevier B.V. All rights reserved.

Estudo da fotossensibilidade de materiais híbridos de sílica dopados com heteropoliânions de tungstênio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)