Doubly patternable epoxy based sol–gel structures by UV and soft lithography

The sol–gel synthesis of hybrid materials offers special opportunities to combine polymer and glass properties and to create promising candidates for photonic applications.We report on the optical and morphological characterization of a new photosensitive epoxy based sol–gel system. Germanium ethoxide and 3-Glycidoxypropyltrimethoxysilane were used as precursors for hybrid sol-gel planar coatings. A photoacid generator was added to solution in order to allow the epoxy photopolymerization when the films are selectively exposed to UV light. The refractive index increase (Δn = 0.015) induced by UV light allows the direct patterning of waveguiding structures having good morphological quality. Stripes and beam splitters were defined by direct UV exposition on silicon substrates. Moreover, we present structures made by thermal imprinting method. Silicon masters have been used to transfer relief gratings on the photopolymerizable epoxy sol-gel materials. Combining thermal imprinting technique and UV light exposition through a photomask, complex structures can be realized such as light couplers, sensors and wavelength filters.     

Water based sol–gel methods used for Bi-222 thermoelectrics preparation

Three different water based sol?Cgel methods were compared in the synthesis of Bi₂Sr₂Co_1.8O_x thermoelectric ceramics. We chose methods that can stabilize a Bi³⁺ ion while solution and gel are formed: chelating method using combination of ethylenediamintetraacetic acid (EDTA) and triethanolamine (TEA) chelating agents and, further, synthesis using two different water soluble polymers??polyacrylamide or polyethylenimin. In each sol?Cgel process, we tested two gel decomposition atmospheres. The gels were decomposed either in air or in inert atmosphere (followed by treatment in pure oxygen). Additionally, a sample synthesized by solid state reaction was used for comparison with the sol?Cgel prepared samples. The grain size of precursors and also their phase composition were determined for methods used and different gels decomposition atmospheres. The sintered final samples did not differ in phase composition; on the other hand, they vary in volume density and microstructure. The differences were reflected in electric transport measurement (the temperature dependence of Seebeck coefficient, resistivity and thermal conductivity). The use of EDTA/TEA or PEI methods led to the samples with improved thermoelectric parameters in comparison to the solid state sample.     

Elimination of porosity in heavily rare-earth doped sol–gel derived silicate glass films

The combination of spin-coating and rapid thermal annealing is a very important sol–gel technique to prepare high quality silicate glass films, widely used in the fabrication of waveguides, photonic bandgap structures and other film-based optical devices. This work found that high rare-earth concentrations will seriously affect the optical quality of the films prepared by the spin-coating/rapid thermal annealing process, with pores with hundreds of nanometres in size being found in heavily rare-earth doped aluminosilicate glass films, causing significant light scattering. However, it was also found that a new recipe using acetylacetone was able to dramatically eliminate these pores and to improve the film optical quality, even for rare-earth concentrations as high as 15 mol%. This result will be useful for the fabrication of sol–gel derived devices based on rare-earth doped silicate glass films like active waveguides, functional films and photonic bandgap structures.     

Nanocomposites based on nickel ferrites dispersed in sol–gel silica matrices

In this work, we describe the effects of thermal treatments on the structural, morphological, and textural properties of nanocomposites formed by nickel ferrite dispersed in xerogel and aerogel silica matrices. The catalytic properties for the total oxidation of an organochloro model contaminant, the chlorobenzene, are also evaluated. Wet samples with different amounts of NiFe₂O₄ in matrix were prepared by sol–gel process. Xerogels and aerogels obtained in monolithic form were prepared by controlled and hypercritical drying, respectively, and heated at temperatures between 300 and 1,100°C. The specific surface area and total pore volume of the samples change with heating mainly due to the variation on their texture. The xerogel treated at 500°C and the aerogel treated at 700°C showed the most catalytic activity, converting chlorobenzene at temperatures as low as 150°C, while the other catalysts were active only at temperatures higher than 300°C. No organic by-products were observed in the oxidation of chlorobenzene, suggesting that total oxidation takes place under the reaction conditions. A strong decrease in catalytic activity was observed for nanocomposites treated at 1,100°C, due to matrix densification, which led to the encapsulation of the ferrite particles and hindered the access of the gas to the ferrite surface.     

Hybrid sol–gel based coatings for the protection of historical window glass

Medieval glass is commonly attacked by atmospheric pollutants conveyed by water, triggering the corrosion process. Current conservation strategies aim to maintain window glass in its original context, and so it is necessary to protect it from further degradation. Sol–gel technology is very effective for the preparation of protective films, using Si-alkoxide precursors chemically similar to the substrate. The present work discusses water-repellent hybrid sol–gel coatings made from tetra-ethyl-ortho-silicate with different quantities of Si-alkoxides, functionalized with various alkyl groups. The coatings were deposited using the dip-coating technique and characterized by UV–VIS and FT-IR spectroscopy. Static and dynamic contact angle measurements showed an overall homogeneity of the coatings and indicated improved water-repellency when functionalized by long alkyl chains. The coatings with best performance in terms of transparency and contact angle, and with the lowest organic content, were selected and applied to medieval-like glass samples. Colorimetric characterization was carried out using a spectrophotometric scanner before and after application of the coatings and no significant color changes were found. The electron microscopy images revealed relatively even, crack-free coatings, especially with higher organic contents. Contact angle and colorimetric measurements were repeated after accelerated ageing by exposure to UV light and an SO₂-saturated atmosphere. A significant decrease in the contact angle was observed only for the samples treated at the highest SO₂ concentration. The silica-based materials did not give reaction by-products, were water-repellent, compatible with the substrate, colorless, transparent, and stable under exposure to chemicals and light, thereby satisfying the main requirements for the conservation of Cultural Heritage.     

Click approaches in sol–gel chemistry

The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies.     

Synthesis of monodispersed lithium silicate particles using the sol–gel method

Lithium silicate particles were prepared by the sol–gel process based on the Stöber method using tetraethoxysilane and lithium ethoxide as starting materials; lithium dodecyl sulfate (LDS) was used as a surfactant. Lithium ion concentration of the obtained particles increased with an increase of Li/Si ratios from 1 to 4. Scanning electron microscope images showed that the obtained particles were rather monodispersed with diameter of 100–300 nm, and the particle size was not influenced by the amount of added LDS but the Li/Si ratios. Fourier-transform infrared spectra of the particles showed that the intensity of the peaks due to CO₃ ^2? increased with an increase of the Li/Si ratios. X-ray diffraction patterns and ²⁹Si magic-angle spinning-nuclear magnetic resonance spectra of the particles indicated that Q₃ and Q₂ units were present as amorphous state in the particles prepared with Li/Si ratios of 1 and 2, respectively. In the case of Li/Si ratios of more than 3, lithium metasilicate crystals formed, and Q₁ and Q₂ units were dominant.     

Fluorescent organic nanocrystal confined in sol–gel matrix for bio-imaging

The sol–gel chemistry combined to a spray-drying process allowed us to control the formation of original hybrid core–shell nanoparticles constituted by molecular nanocrystals of rubrene embedded in biocompatible silicate spheres. With a good management of all the physical (gas flows, temperatures) and chemical (dye, solvent and alkoxide natures, concentrations, and hydrolysis and condensation conditions) parameters, we optimized a one-step and self-assembly process allowing to obtain nanoparticles exhibiting promising optical properties such as highly fluorescent labels (two-photon excitation) for medical imaging. Moreover, the presence of Si–OH functions on the silicate shell surface make easy to functionalize these fluorescent nanoparticles by grafting biomolecules for targeting properties. The confined nucleation and growth of rubrene nanocrystals in sol–gel silicate spheres during their drying in the air laminar flows, prevents any phase segregation or particle coalescence and stabilizes mechanically and chemically the organic cores. The first particle sizes obtained in these first experiments are ranging between 80 and 600 nm, but lower diameters will be easily prepared by increasing the solvent amount. Transmission electron microscopy was used to characterize the rubrene organic cores. The electron diffraction patterns performed at 100 K, under low-dose illumination to avoid amorphization of the samples during electron irradiation, have shown the good crystallinity of the NP rubrene cores that seem to be constituted by single rubrene nanocrystals. Finally, optical confocal microscopy, used in reflection and fluorescence modes, showed that all the core–shell particles are strongly fluorescent. This high fluorescence intensity arises from the high molecule numbers of rubrene nanocrystals, which enhance the absorption and emission cross sections.     

Microwave-assisted sol–gel synthesis for molecular imprinting

Molecularly imprinted polymers have been the subject of intense research for several decades in both academic and industrial settings. In this paper, we introduce a novel microwave-assisted sol–gel method for molecular imprinting of silica microspheres. The microspheres were characterized, and their adsorption of imprint and non-imprint molecules was investigated. The dye molecules methyl orange and ethyl orange were used as templates. Good molecular imprinting was observed as evaluated by the re-adsorption of dye into the silica matrix followed by the removal of dye from the supernatant solution.     

X-rays to study,induce, and pattern structures in sol–gel materials

X-rays investigations have been shown to reveal important information regarding material features and the formation mechanism of mesostructured materials. Small angle X-ray scattering (SAXS) analysis performed using a synchrotron source has been very important in the optimization of the organization of mesoporous coatings obtained by evaporation induced self-assembly (EISA). The interaction between X-rays and ordered mesoporous films has only recently been reported, and new knowledge has been developed to use this external radiation source to tune the local material properties. Here we discuss the recent developments in X-ray lithography combined with sol–gel synthesis to pattern mesostructured and hierarchical porous coatings including the ability to tailor functionalized surfaces.     

Lactic acid based sol–gel process of Ag nanoparticles and crystalline phase control of Ni particles in aqueous sol–gel process

Nickel and silver particles were prepared by using sol–gel auto-combustion method under N₂ atmosphere where lactic acid was applied as chelating agent. The synthesis of nickel particles was carried out at various pH conditions (2–7), resulting in the face-centered-cubic or hexagonal-close-packed crystalline nickel phase. The morphology and structure of synthesized nickel particles and silver nanoparticles were characterized by X-ray diffraction, transmission electron microscope, energy dispersive X-Ray spectroscopy and differential scanning calorimetry-thermogravimetric analysis. The results show that the spherical Ag nanoparticles with diameters in the range of 18–27 nm and narrow size distribution can be obtained by this sol–gel process.     

Electron beam writing of epoxy based sol–gel materials

We report the use of an epoxy based hybrid sol–gel material as negative resist for electron beam lithography (EBL). The matrix has been prepared starting from 3-glycidoxypropyltrimethoxysilane as specific organic–inorganic precursor and the synthesis has been strictly controlled in order to preserve the epoxy ring and to obtain a proper inorganic cross-linking degree. The film has been exposed to an electron beam, inducing the polymerization of the organic part and generating the film hardening. Preliminary results of a resolution test on the synthesized epoxy based sol–gel material, performed with electron beam lithography, are presented. Structures below 300 nm were achieved. The direct nanopatterning of this hybrid sol–gel system simplify the nanofabrication process and can be exploited in the realization of photonic devices. A demonstration has been carried out doping the hybrid films with commercial Rhodamine 6G and reproducing an already tested laser structure.     

Advanced sol–gel coatings for practical applications

One of the features of the sol–gel techniques is closeness to the industrial applications. Another feature is the variation of shapes of obtained materials like bulk, fiber, coating film, powder and so on. Among them, the author has focused on research of the sol–gel coatings on various substrates for practical applications as well as the fundamental research under the collaboration with industry. In this review, results of such research will be presented. These include (a) protective coating on metal sheets, (b) micropatterning on glass substrates, (c) water-repellant coating on windshields, (d) colored coating on glass bottles for easy recycling, (e) superhydrophobic and superhydrophilic coating on glass plates, and (f) anti-reflective coating on glass lenses for cameras. Some were highly successful, and some were not, of course. The author also contributed to the foundation of The Japanese Sol–Gel Society in 2003. The activities of The Society in these 8 years are introduced.     

Activity modulation and reusability of β-d-galactosidase confined in sol–gel derived porous silicate glass

In the present work we applied the sol–gel method to obtain glass lentils entrapping β-d-galactosidase (β-Gal) (E_β-Gal) within a silicate matrix. The effect of pH, temperature, polarity and salt concentration on the activity of E_β-Gal was studied. Apparent kinetic parameters for ortho-nitro-phenyl-β-d-galactopyranoside hydrolysis catalyzed by E_β-Gal $({V^{\prime }}_{\text{max}},{K^{\prime }}_{\text{M}})$ were lower compared to the soluble enzyme (S_β-Gal), reflecting the solute diffusion restriction imposed by the matrix observed in the time curves, a partial protein inactivation upon encapsulation, and an improvement in the affinity of E_β-Gal for the substrate as compared with S_β-Gal. At pH < 4, E_β-Gal stability was higher than that of S_β-Gal. E_β-Gal could be reused after storage at 4 °C for up to 90 days, and retained its activity profile within the range of pH = 2–10 and saline concentration 0–400 mM. Pre-incubation at 75 °C for 30 min fully inactivated S_β-Gal while E_β-Gal retained approximately 90% of its activity, even in the reused samples. Encapsulation did not introduce additional impairments to the reaction rate measured in heterogeneous dispersions, beyond those derived from their own particle-crowded environment. This reusable E_β-Gal was resistant to typical technological conditions applied in milk processing that would lead to the unfolding and inactivation of S_β-Gal. The results are discussed from the biophysical viewpoint.     

Formation and characterization of phosphate-modified silicate materials derived from sol–gel process

Phosphate-containing silicate materials prepared using sol–gel method from Si(OC₂H₅) were investigated at the variation of the amount of phosphate modifier from 5 to 50 wt% in term of P₂O₅. Chemical composition, textural and structural properties of these materials were characterized by FTIR-spectroscopy, TEM, X-ray diffraction and nitrogen adsorption. It was shown that the materials posse monomodal pore size distribution of 5–20 nm for the samples dried at 100 °C and 40–60 nm for the specimens calcined at 600 °C. The mean pore size and surface area depended on the amount of phosphoric acid. Before the stage of high temperature treatment phosphoric acid, introduced into the structure of the materials as a modifying agent, was uniformly distributed inside a porous space of the material and was not chemically bonded with silicate. After high temperature treatment both chemical interaction of silicate with phosphate, providing the formation of silicate-phosphate structures, as well as redistribution of free modifier from the bulk of granules to their surface took place. The polyphosphate layer is formed on the material surface closing the internal porous space. However, in this case a part of the phosphate modifier remains chemically unbound to SiO₂ structure.     

Surface plasmon resonance biosensor based on Au nanoparticle in titania sol–gel membrane

A novel surface plasmon resonance (SPR) biosensor for the determination of human IgG was introduced. The biosensor was prepared with three layers of titania sol–gel membrane by vapor deposition. The colloid Au nanoparticle (AuNP) was immobilized in the second layer of titania membrane and the AuNP coupled with rabbit anti-human IgG was encapsulated in the third layer. The AuNP in the second layer of titania membrane was proved to be effective in the sensitivity enhancement of SPR biosensor. The lowest concentration that could be detected obtained by the biosensor with AuNP is about eight times lower than that obtained without AuNP. In addition, the titania sol–gel is a porous homogeneous material that permits analytes to access the encapsulated biomolecule and can provide a controlled environment for the study of biomolecular recognition. The titania sol–gel was also confirmed to be benefit for biomolecule to keep bioactivity, which could offer a good waterish microenvironment. As a result, the modified biosensor exhibits a satisfactory response for human IgG in the concentration range of 0.30–40.00 μg mL^?1 and shows favorable bioactivity for a long time.     

Ionic liquid-mediated sol–gel coatings for capillary microextraction

Ionic liquid (IL)-mediated sol–gel hybrid organic–inorganic materials present enormous potential for effective use in analytical microextraction. This opportunity, however, has not yet been explored. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol–gel reactions. In this work, we developed a method that overcomes this hurdle and provides IL-mediated advanced sol–gel materials for capillary microextraction (CME). We examined two different ILs: (a) a phosphonium-based IL, trihexyltetradecylphosphonium tetrafluoroborate, and (b) a pyridinium-based ionic liquid, N-butyl-4-methylpyridinium tetrafluoroborate. These ILs were evaluated in conjunction with two types of hydroxy-terminated polymers: (a) two Si–OH terminated polymers (PDMS and BMPO), and (b) two C–OH terminated polymers (PEG and polyTHF) that differ in their sol–gel reactivity. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol–gel reactions. The IL-mediated sol–gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions in off-line CME-GC compared to analogous sol–gel coatings prepared without any IL in the sol solution. Contrary to this, the IL-mediated sol–gel coatings prepared with C–OH terminated polymers provided lower extraction efficiencies compared to their IL-free counterparts. These observations were explained by (a) lower sol–gel reactivity of C–OH groups in PEG and polyTHF compared to Si–OH groups in PDMS and in hydrolyzed alkoxysilane precursors and (b) extremely high viscosity of ionic liquids. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol–gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol–gel material to be able to provide the desired sorbent characteristics. Additionally, IL-mediated sol–gel PDMS coatings provided run-to-run RSD values of 4.2–5.0% and detection limits ranging from 3.2 ng/L to 17.4 ng/L. PDMS sol–gels prepared without ILs provided RSD values of 2.8–14.1%, and detection limits ranging from 4.9 ng/L to 487.0 ng/L.     

Acid–base sensor based on sol–gel encapsulation of bromothymol blue in silica: application for milk spoilage detection

Journal of Sol-Gel Science and Technology - In this work, silica capsules containing bromothymol blue (BTB) were synthesized by a modified Stöber sol–gel method. These silica capsules...     

Optically transparent silica aerogels based on sodium silicate by a two step sol–gel process and ambient pressure drying

Interest in improving the optical transmission of sodium silicate-based aerogels by ambient pressure drying led to the synthesis of aerogels using a two-step sol–gel process. To produce optically transparent silica aerogel granules, NH₄F (1 M) and HCl (4 M) were used as hydrolyzing and condensation catalysts, respectively. The silica aerogels were characterized by their bulk density, porosity (%), contact angle and thermal conductivity. Optical transmission of as synthesized aerogels was studied by comparing the photos of aerogel granules. Scanning electron microscopic study showed the presence of fractal structures in these aerogels. The degree of transparency in two step sol–gel process-based aerogels is higher than the conventional single step aerogels. The N₂ adsorption–desorption analysis depicts that the two step sol–gel based aerogels have large surface areas. Optically transparent silica aerogels with a low density of ∼0.125 g/cc, low thermal conductivity of ∼0.128 W/mK and higher Brunauer, Emmett, and Teller surface area of ∼425 m²/g were obtained by using NH₄F (1 M), HCl (4 M), and a molar ratio of Na₂SiO₃::H₂O::trimethylchlorosilane of 1::146.67::9.46. The aerogels retained their hydrophobicity up to 500 °C.