Sol–gel technology for functional finishing of PES fabric by stimuli-responsive microgel

The possibility of incorporating a stimuli-responsive microgel into a silica matrix by the sol–gel method was studied. This method allows the preparation of a novel class of functional finishes for textile material modification, which is aimed at the creation of simultaneous stimulus-responsive behaviour and functional protective properties. Using a pad-dry-cure method, a thermo- and pH-responsive microgel (PNCS) based on poly-(N-isopropylacrylamide) (poly-NiPAAm) and chitosan was embedded into a silica matrix on a previously activated polyester (PES) fabric. The matrix was composed of a model sol–gel precursor, vinyltrimethoxysilane (VTMS), in combination with hydrophilic fumed silica nanoparticles (SiO₂). Functionalized PES fabric samples were characterised by determining the morphological and chemical properties using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The stimuli (temperature and pH) responsiveness of the functionalized PES fabric was established by measuring its porosity, wicking ability, moisture content, drying rate, water vapour transmission rate and water uptake. In order to assess the washing fastness of the surface modifying systems, the tests were done before and after five consecutive washings. The results showed that sol–gel technology is an appropriate method for the incorporation of PNCS microgel on PES fibre surface. Because of the elasticity of the sol–gel matrix, the VTMS/SiO₂ polysiloxane film had no adverse influence on the swelling/deswelling effect of the PNCS microgel, thus retaining and even enhancing its stimulus response.     

Sol–gel technology and template synthesis in thin gelatin films

Processes of sol–gel technology of template synthesis of 3d-element metal macrocyclic complexes that occurs in thin films of metalhexacyanoferrate(II) gelatin-immobilized matrix implants under their contact with water solutions containing various (N,O,S)-donor atomic and (C=O) containing organic compounds, have been discussed. It was noted that, in a series of cases, sol–gel technology of template synthesis in the given specific conditions allows to realize such metal macrocyclic complexes formation processes that are not typical at the complexing in solutions or solid phase.     

Sol–gel thin films for optics and photonics

Thin films have wide applications in the area of optics and photonics. Conventional thin film processing is usually followed for deposition, but the sol–gel route is unique as it can be applied very easily in a cost effective way on desired substrates of any shape for specific applications. In this review, the basic optical designs of antireflection, high reflection, different types of optical filters, coloured coatings, etc. have been discussed with some typical examples of sol–gel products. The importance of coloured coatings and low thermal emissivity coatings on window glass has also been highlighted. In addition, the use of sol–gel processing for different types of film formation which are effective for photonic applications such as non-linearity in optics, ferromagnetism in transparent dilute magnetic semiconductors (DMS), generation of quantum dots as phosphor, grating coupler waveguide in optical sensors are discussed. The basic characterizations of a few sol–gel products which may be used for photonic applications have also been highlighted.     

Sol–gel technology as representative processing for nanomaterials: case studies on the starting solution

In order to fabricate sol–gel products with desired microstructure in the form of bulk, fiber and coating film, the appropriate selection of the composition of the starting solution is of primary importance. In this paper, the effects of the composition of the starting solution on the reaction in alkoxysilane solutions, the formation of bulk and fiber, and the microstructure of a particular coating film are reviewed, based on our experiences. It is shown in the alkoxysilane and alkylalkoxysilane solutions that, besides hydrolysis and random polymerization, various reactions take place. Among them, the formation of a four-membered ring molecule in dimethyldialkoxysilane solution, formation of a cage-like cubic octamer in an tetraalkoxysilane solution containing, for example, tetramethylammonium ion and stabilization of a solution for polycomponent oxides by the addition of tartaric acid are discussed. It is also shown that the composition of the starting solution suitable for fiber drawing is different from that for the formation of crack-free bulk gels: for the fiber drawing acid catalyst and low water content are required in various oxide systems including silica, while for the bulk silica gels ammonia-catalyzed alkoxysilane solution with dimethylformamide solvent or highly acidic solution works well for bulk silica gel. Finally, it is shown that the control of microstructure of coating films can be realized by selecting the composition of the starting solution. As an example, the change of the acid content of the starting solution produces three different microstructures of polycrystalline, crystal-oriented and amorphous structure in the lithium borate coating film. As another example, the size of precipitated noble metal particles in the coating film is controlled by the water and acid content of the solution. The mechanism of the above phenomena is also discussed.     

Sol–gel derived durable antireflective coating for solar glass

In this paper, we present the design and preparation of a type of high-strength SiO₂/TiO₂ AR coatings used in solar glass by dip coating method. The average transmittance of glass coated in this way is increased by more than 6% in the wavelength from 400 to 800 nm, which fits well with the theoretical expectation. The mechanical performance and atmospheric exposure tests prove that the coatings have scratch resistance, erosion resistance and long-time stability. The AFM morphology shows that the surface of the coating is very smooth with the experimental result of RMS roughness 0.306 nm. These phenomena indicate that the SiO₂/TiO₂ AR coatings have high potential commercialization for low-cost solar glass.     

Sol–gel derived dye-bridged hybrid materials for white luminescence

Novel yellow and blue emissive dyes have been synthesized using 2,5-diamino-3,6-dicyanopyrazine and various alkoxysilanes and they are covalently bridged to cycloaliphatic epoxy functional oligosiloxane via non-hydrolytic sol–gel reaction. Dye-bridged hybrid materials (DBH) are fabricated by thermal curing the dye-bridged oligosiloxane. Structure and formation of dyes and siloxane network is studied using analysis method. Four components of red, yellow, green and blue emitting DBH cover entire visible range and white luminescence with high color rendering index is realized by controlling their combinations. We have ensured superior thermal stability DBH at 120 °C for 200 h caused by covalently bridged structure and robust siloxane matrix.     

Sol–gel research in Italy

A short story of the research on sol–gel in Italy is given, and the evolution is presented and compared with the rest of the world in terms of number of publications, citations and patents. It is shown that both basic and applied research are active and effective in Italy.     

Sol–gel derived ZnO/porous silicon composites for tunable photoluminescence

ZnO/porous silicon nanocomposites were fabricated by spin-coating the sol?Cgels of zinc acetate onto the top surface of porous silicon films. The photoluminescent properties of ZnO/porous silicon nanocomposites were investigated as a function of the concentration of zinc cations in the sol?Cgels. Characterizations with scanning electron microscopy, X-ray diffractometry and photospectroscopy indicated that ZnO nanocrystals were embedded into the spongy nanostructures of porous silicon after heat treatment at 245?°C for 20?min in air. The recorded photoluminescence exhibited that orange to green?Cblue emissions were achieved for the ZnO/porous silicon nanocomposites as the concentration of zinc cations in the sol?Cgels increased from 4 to 260?mM. The mechanisms on the tunability of the photoluminescence were discussed for the ZnO/porous silicon nanocomposites. Our results have demonstrated that the incorporation of green?Cblue phosphors into the porous matrix of porous silicon represents one endeavor to tune the photoluminescence of porous silicon across the visible spectral region.     

Sol–gel behavior of a novel nanodroplet biomaterial for drug delivery

Nanodroplets can be considered as those nano/microemulsions in which the oil itself forms the active agent and the droplet size ambits in the nanometer range. Eugenol is an anti-inflammatory agent and its nanodroplet gel (NDG) has immense potential for topical use. Topical gels oblige some rheological characteristics to nail down the demands of proper application, stability and storage. Thus, the purpose of our study was to comprehend the effect of eugenol on the sol–gel tranisition properties of its NDGs. Towards this goal nanodroplets of eugenol were prepared and evaluated and the three selected nanodroplet formulations with 5, 10 and 5% v/v eugenol were converted into topical gel formulation using 1% w/w Carbopol 940. The NDGs were characterized using frequency sweep, creep recovery and thixotropy. All these tests pointed out that eugenol concentration has significant effect on the sol–gel behavior of NDGs. The NDGs exhibited more viscous (sol) properties than elastic (gel) properties as observed from the frequency sweep studies. The thixotropy of the NDGs was found to decrease with increase in eugenol concentration. Efforts have been made to explain the study results using mechanistic approach. The outcomes of our research studies could be of great use in future endeavors towards development of a topical NDG of eugenol with tailored sol–gel behavior.     

Sol–gel preparation of aminopropyl-silica-magnesia hybrid materials

A series of aminopropyl-silica-magnesia hybrid materials has been prepared by the sol–gel method from tetraethoxysilane (TEOS), magnesium chloride (MgCl₂) and aminopropyltriethoxysilane (APTES) under acid conditions. The APTES:TEOS ratio was varied between 0:1 and 1:0. The aminopropyl coverage concentrations for APTES-silica-Mg samples were in the range of 0.3–2.3 mmol g⁻¹. The hybrid materials were characterized by numerous techniques, including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman), solid-state ¹³C and ²⁹Si nuclear magnetic resonance (¹³C- and ²⁹Si-NMR), thermogravimetry (TGA), N₂ adsorption–desorption, small-angle X-ray scattering (SAXS), and scanning electron microscopy (SEM). The increase of APTES content in the silica network resulted in the increase of six-membered siloxane rings. The hybrid systems were shown to be formed from fully-condensed, trifunctional APTES species. The porosity and morphology of the hybrid materials were influenced by the initial TEOS/APTES ratio. The radius of gyration of the primary particles, determined by SAXS, was between 1.1 and 2.9 nm.     

Sol–gel combustion synthesis of BNBT powders

Ba-modified bismuth sodium titanate with composition 0.94[(Bi_0.5Na_0.5)TiO₃]-0.06BaTiO₃ (BNBT) was prepared by a citrate nitrate sol–gel combustion method. The sol was obtained using barium acetate, bismuth nitrate, sodium nitrate and a peroxo-citrate complex of titanium isopropoxide as starting precursors. Various molar ratios of citrate/nitrate (C/N) were considered for the sol production. The corresponding gels were fired at different temperatures (300, 400, 500 °C) in order to evaluate the conditions necessary to obtain the decomposition of the precursors and the formation of the pure BNBT perovskitic phase in a single step. The best conditions to obtain the desired phase are: (C/N) = 0.2, and combustion temperature of 500 °C. Ball milled powders were densified at a temperature 100 °C lower than the one generally used for powder produced with the conventional mixed oxide route. The electrical properties are comparable to those reported for conventionally prepared materials.     

Sol–gel silica hybrid biomaterials for application in biodegradation of toxic compounds

The purpose of the present work is the sol–gel synthesis, structure characterization and potential application of hybrid biomaterials based on silica precursor (MTES) and natural polymers such as gelatin or pectin. The structure formation in the biomaterials was investigated by XRD, FTIR, BET and AFM. The results showed that all studied hybrid biomaterials have an amorphous structure. The FT-IR spectra of the obtained materials with MTES showed chemical bonds at 2,975, 1,255, 880 and 690 cm⁻¹ due to the presence of Si–O–R (CH₃ and C₂H₅) and Si–C bonds. In the samples synthesized with TEOS the inorganic and organic components interact by hydrogen bonding, Van der Waals or electrostatic forces. Surface area of investigated samples decreases with increasing of the natural polymers content. The structure evolution was studied by AFM and roughness analysis. Depending on the chemical composition a different design and size of particles and their aggregates on the surface structure were established. The hybrid biomaterials were used for immobilization of bacterial cells and applied in the biodegradation of the toxic compound 4-chlorobutyronitrile, possible constituent of waste water effluents in a laboratory glass bioreactor. Optimization of the process at different temperatures was carried out.     

Sol–gel synthesis of porous titania fibers by electro-spinning for water purification

In this study, porous ceramic fibers were prepared by the sol–gel-assisted electro-spinning process using colloidal dispersion of complex fluids for the application of phtotocatalysts. First, polystyrene nanospheres were synthesized by dispersion polymerization as sacrificial templates for porous fibers. Then, the mixture of polyvinylpyrrolidone and the ceramic precursor with the polymeric nanospheres was prepared as the spinning solution and self-organized by electro-spinning, followed by calcination of the electrospun composite fibers. The morphologies of the porous fibers could be controlled according to the size of the templates and the amount of the ceramic precursor. The nano-structure of the pores in the fibrous materials could also be adjusted as open or closed cavities with various potential applications. As a demonstrative application, the macroporous titania fibers could be utilized as photocatalysts for the removal of organic dyes dissolved in water. A better photocatalytic activity of the macroporous fibers with 700-nm pore diameter was observed compared to the result of nonporous titania fibers due to the increased porosity. Collectively, the macroporous ceramic fibers were found to be efficient functional materials to prepare the unique nano-structured materials other than simple nonporous fibers.     

Sol–gel chemistry of an aqueous precursor solution for YBCO thin films

A water based YBa₂Cu₃O_7−x (YBCO) precursor using a triethanolamine (TEA)/acetic acid complexing method to obtain YBCO thin films is described in detail. The influence of complexation behavior in the formation of transparent and homogenous sols and gels after the combination of Y, Ba and Cu—acetates, acetic acid and TEA has been studied by potentiometric titration and the results are compared with analytical simulations. The decomposition of the gel was studied by IR (infrared) and Thermal Gravimetric Analysis/Differential Thermal Analysis (TGA/DTA). The results in sol-gel chemistry can be used to decide on the necessities in the preparation of stable sol–gel precursors with a minimum amount of organic compounds. The sol–gel system was also used for the deposition of high textured superconducting thin films on STO substrates by dip coating. The synthesized YBCO showed a superconducting transition temperature of 90.95 K with narrow ΔT (2 K) for thin films. The results from X-ray diffraction show that the single phase YBCO was obtained. SEM pictures also indicate that the properties of the surface thin films are good.     

Sol–gel nanohybrid materials prepared via supramolecular organization

This article reports on recent progress in the synthesis of sol–gel nanohybrid materials based on the supramolecular organization. A variety of nanohybrid materials has been obtained by molecular design of the precursors and systematical control of synthetic processes. Organoalkoxysilanes with covalently attached hydrophobic tails are hydrolyzed to form amphiphilic molecules containing silanol groups, leading to the formation of vesicular structures. The obtained hybrid has analogous structures of both cell membrane and silica particle and was named “cerasome”. The cerasome can achieve the hierarchical three-dimensional organization of vesicular particles on the substrate. The nanohybrids are developed not only by the hydrophobic interaction of amphiphilic molecules but also by the electrostatic interaction. The layer-by-layer (LbL) assembly of the water-soluble titania precursor with polycation is adopted for nanohybrid coatings containing titania nanoparticles on the substrates. In addition, preparation of hybrid hollow capsules via LbL assembly and sol–gel method with colloid templating is also discussed.     

Sol–gel composite coatings from methyltriethoxysilane and polymethylhydrosiloxane

New composite coatings were prepared by mixing pre-hydrolyzed methyltriethoxysilane (MTES) sol by an acidic catalyst dibutyltin dilaurate (DBTDL) and polymethylhydrosiloxane (PMHS) in gasoline at room temperature. The gel process was thoroughly investigated regarding the use of different basic catalyst [3-aminopropyltriethoxysilane (APTES) or triethylamine (TEA)], as well as the ratios of pre-hydrolyzed MTES sol and PMHS with various content of active H. It was revealed that the composite coating from 2:1 ratio (w/w) of pre-hydrolyzed MTES sol with equimolar amounts of water and PMHS_1.55 under the catalysis of APTES demonstrated high pencil hardness, and excellent resistance against contamination and corrosion. This composite coating (MTPM21-A) was further characterized by FTIR, ²⁹Si NMR, DSC and TGA.     

Sol–gel preparation of double-layer tri-wavelength antireflective coating

Double-layer tri-wavelength antireflective (AR) coating effective simultaneously at 351, 527 and 1,053?nm has been designed and prepared by the sol?Cgel process. The refractive index and film thickness of bottom layer and up layer are 1.27 and 113?nm, and 1.17 and 245?nm, respectively. The bottom layer with refractive index of 1.27 was prepared from a mixture of acid-catalyzed and base-catalyzed silica sols, and the up layer with refractive index of 1.17 was prepared from polypropylene oxide modified silica sol. It was found that the addition of polypropylene oxide into the sol significantly decreased the refractive index and increased the hydrophobicity of the AR coating. The obtained tri-wavelength AR coating gives very high transmittance of 99.7, 99.1 and 98.0?% at 351, 527 and 1,053?nm, simultaneously.