Vegetal nanoclusters in hybrid silica films prepared by sol-gel spin coating technique

Hybrid sol-gel films containing Rosemary extract nanoclusters embedded into hybrid silica network have been successfully synthesized using the sol-gel procedure by exploiting the template route, in association with an adequate spin-coating method. Formation of film precursor sols and effect of selected amounts of octyl trimethoxysilane and ethyl oleate succinic anhydride into the starting acid sols on the sol-gel product size have been evaluated by dynamic light scattering technique. The spectral characteristics of hybrid organic-inorganic films have shown that the multiple functional groups from Rosemary extract associated with residual Si-OH groups can cause the increase in the degree of physical interaction. The effect of hybrid sols meaning the silica precursors molar ratio and template concentration on the fluorescence of hybrid films has been also investigated. The fluorescence properties of synthesized films were found to be dependent on template and natural extract concentration. A higher amount of template resulted in doubling the fluorescence intensity in the 400-480 nm domain. The microstructural characteristics of the hybrid films revealed by atomic force microscopy have shown a homogeneous surface morphology with cluster-like structure. Hybrid silica films exhibit a periodic structure with cluster size less than 150 nm.     

Fluorescence properties of a ruthenium complex in silane sols and gels at different pH

Silane gels containing ruthenium Ru(bpy)₃²⁺ complex were obtained by the sol-gel method. The gelation of sols at different pH values was monitored by fluorescence stationary and time-resolved measurements. In all tested sols a blue shift of fluorescence emission maximum of the fluorophore was observed during the gelation. Changes in λ_max on subsequent days of sol-gel transition depended on starting pH of the sol. An increase of the excited state of fluorophore lifetime in the gelation process was observed. When the gelation was finished the lifetime τ₁ was constant. A strict correlation between the blue shift of fluorophore emission maximum and changes in the lifetime of ruthenium complex in this system on subsequent days of the sol-gel transition was observed. On this basis, changes in the fluorophore microenvironment in the sol induced by different rates of competing hydrolysis and condensation reactions were discussed.All observed effects were attributed to the interaction of molecules of the ruthenium complex with hydroxyl groups in the gel net.     

Formation of nanoporous and nanocrystalline anatase films by pyrolysis of PEO–TiO2 hybrid films

Poly(ethylene oxide)–titania (PEO–TiO₂) organic–inorganic hybrid films were synthesized through a sol–gel process and spin coating. The mixed precursor sols were aged for 6 and 12 h, respectively, prior to the spin coating. Hybrid films were crystallized to the anatase phase first and then further heat treated at elevated temperatures for different time periods to analyze the anatase-to-rutile phase transformation. Quantitative X-ray diffraction (Q-XRD) results were employed for Johnson–Mehl–Avrami (JMA) kinetic analyses and the Avrami exponent (n) was determined for each film. The Arrhenius plots were created based on the JMA plots and the activation energy (Q) values for the phase transformation were determined for each film. The difference in the phase transformation kinetics in the films was discussed based upon the difference in the activation energy values and thus the molecular structures of each hybrid film. Nanoporous and nanocrystalline anatase films were successfully achieved through the retarded phase transformation during the pyrolysis of the organic–inorganic hybrid films. Owing to the maximized surface area these nano-structured anatase films are highly expected to show the enhanced photocatalytic efficiency compared to common TiO₂ films as well as sintered bulk forms.     

Rheology of the gelation of fluorine-doped silica sols

Dynamic oscillatory shear measurements are used to probe the gelation kinetics of aqueous sols composed of either particulate silica or silicon alkoxide solution. Unlike steady shear measurements, these dynamic tests do not alter the structure and kinetics of the sol-gel process. The dynamic storage moduli of both systems show sharp transitions at the onset of gelation. However, the gelation kinetics of the two systems are very different; the modulus of alkoxide system remains unchanged until the gel point is reached, whereas that of the particulate system increases with time even below the gel point as the colloid cluster grow. Unlike the alkoxide gel, the particulate gel reverses to a sol upon shearing. The gelation kinetics of a resheared sample is slower than that of a fresh sample. The structures associated with the sol-gel transition for this particulate system have been monitored using freeze fracture microscopy and correlate with rheological observations. The gelation times for both sols are varied by changing the fluoride ion content.     

Spinnablity and structure characterization of mullite fibers via sol–gel-ceramic route

Viscosity and rheology behaviors of the mullite sols prepared from aqueous solution of aluminum nitrate, aluminum isopropoxide and tetraethylorthosilicate has been investigated. Rheological measurement suggested that mullite sols exhibited good spinniabilty when the evaporation of the solvent is allowed during sol–gel process. Spinnable sols showed shear-thinning flow behavior with high viscosity to the time of gelation. By adjusting temperature, the gelation degree and viscosity of the sol could be stabilized at a certain value and the sol–gel transition could be transferred to the spinning line of a laboratory dry-spinning apparatus. Continuous mullite fibers were obtained from such sols using sol gel dry-spinning method. The final ceramic fibers had smooth surfaces with an average diameter of 50 μm. Structure evolution of mullite ceramic fibers were characterized by MAS NMR and specific surface area analyses.     

Spectroscopic characterization of intrinsic losses in an organic-inorganic hybrid waveguide synthesized by the sol-gel process

A promising way of fabricating integrated optics components is based on the sol-gel synthesis and photocuring of hybrid materials. However, the presence of OH groups in these materials is a major factor in optical amplification inhibition. In particular, high losses at 1550 nm are mainly due to non-condensed OH groups originating from the sol-gel process at low temperature. Thus, improvement of the final properties of these materials is correlated with the inhibition of OH group concentration. In this study, we used ²⁹Si NMR and near infrared spectroscopy to demonstrate the catalytic effect of zirconium (IV) n-propoxide on the condensation reactions of silanol groups. ²⁹Si NMR showed the absence of silanol species at the end of the synthesis. This result is attributed to the zirconate hydrophilic effect which consumes OH groups by catalysing the polycondensation of Si-OH bonds. In parallel, near-infrared experiments showed the presence of a high proportion of OH species at the end of the synthesis showing that the remaining OH groups are only present in the zirconium species.     

Organic–inorganic hybrid coatings for corrosion protection

The corrosion resistance of sol–gel derived, organic–inorganic, silica-based hybrid coatings with various amounts of organic content was studied. Hybrid sols were prepared by copolymerizing tetraethylorthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPS) with a two-step acid-catalyst process. Hybrid coatings were dip-coated on 304 stainless steel substrates and annealed at 300 °C for 30 min. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. The adhesion and flexibility of the coatings were characterized. The influences of the amount of organic component incorporated into the coatings and the aging of sols on corrosion protection were studied. Electrochemical analyses showed that the relatively dense hybrid coatings provided excellent corrosion protection by forming a physical barrier, which effectively separated the anode from the cathode. Some preliminary biocompatibility tests were also conducted on the hybrid coatings.     

Preparation of organic-inorganic nano-composites for antireflection coatings

In this research, bi-layer thin film stacks that served as an antireflective coating were developed. The top layer was synthesized using tetraethoxysilane and 3-(trimethoxysilyl) propyl methacrylate by the well-known sol-gel technique. Its refractive index was lower than that of the bottom layer, which was prepared by reaction between tetrabutoxyltitanium and γ-glycidoxy propyl trimethoxysilane. Antireflective coatings were obtained by spin-coating of the synthesized sols on a glass substrate, followed by pre-drying, UV-curing, and post-baking. Fourier transform infrared spectrometer was employed to investigate the evolution of chemical bonds during the UV-curing and the sol-gel processes. The size of the inorganic/organic hybrid particles in the sol was found to be less than 10 nm, as measured by transmission electron microscope and dynamic light scattering. Thermo gravimetric analyzer was used to find out the thermal degradation temperature of the two layers and the effect of post-baking. The results indicated that the thermal stability increased after post-baking at 200 °C for 15 min. The reflectance of the antireflection coating was controlled by the relative refractive indices and the thickness of the top and bottom layers. Under optimal synthesis condition, we obtained an antireflection coating, exhibiting a low reflection, 1% at 550 nm, in the visible range.     

Formation of silica/epoxy hybrid network polymers

Epoxy-based inorganic–organic hybrid polymers, for use as a matrix in coatings, have been prepared from 3-glycidoxypropyltrimethoxysilane by a sol–gel process. The precursor molecule possesses both epoxy and silicon alkoxide functionality and so interlinked inorganic–organic networks can be formed. Diethylenetriamine was used to open the epoxy rings and form the organic network to an extent determined by the initial ratio of amine to epoxy groups. The materials were cured either at room temperature or with an additional heat treatment at 150 °C. Structural characterisation of the cured hybrid materials was performed using a combination of Raman, and ²⁹Si and ¹³C MAS NMR spectroscopies. These show that the formation of the two networks does not occur independently and the rate or extent of organic cross-linking has a direct effect on the extent of the inorganic network formation, and vice-versa.     

A comparative FTIR study of thermal and photo-polymerization processes in hybrid sol-gel films

Controlling the organic polymerization in organic-inorganic hybrids is a key point in the development of new materials with high homogeneity of the nanostructure. The main difficulty is related with the achievement of a simultaneous control of the organic and inorganic network formation. Thermal and photocuring represent the main routes to form the organic chains when polymerizable organic groups are present in the hybrid materials. In the present work hybrid organic-inorganic films were synthesized from 3-methacryloxypropyltrimethoxysilane (MPTMS) cohydrolyzed with tetraethylorthosilicate (TEOS) and N-[(3-trimethoxysilyl)propyl]ethylenediamine (TMESPE) or 3-(triethoxysilyl)-propylamine (TESPA). This an example of basic catalyzed hybrid material with a polymerizable methacrylate functionality whose micro-structure is modified by the amine groups. FTIR spectroscopy was used to compare the effects of thermal or photo-induced polymerization on the materials. TESPA and TMESPE showed a different catalytic effect on the condensation of the inorganic network, with TMESPE the more efficient one. The presence of a more extended silica backbone reduced the curing efficiency in TMESPE derived samples. UV curing was also very effective in catalyzing the inorganic condensation of un-reacted species still present in the film after the deposition. A photo-induced polymerization of the inorganic side was observed in the hybrid films. Thermal polymerization in TMESPE films induces the reaction between the secondary amine and CO bonds in MPTMS, this reaction is, instead, not observed in films cured by UV radiation.     

Fabrication of inorganic–organic hybrid films for optical waveguide

Inorganic–organic hybrid guiding and buffer layers for optical waveguides were synthesized by the sol–gel process. An acid-catalyzed solution of 3-(trimethoxysilyl)propylmethacrylate and tetraethylorthosilicate was used as a precursor to produce thick films by spin-coating. Incorporation of a UV-sensitive functional group leads to the fabrication of the photo-patternable guiding layer. High-resolution patterned films with 8 μm linewidth were obtained using a conventional photo-lithography. Furthermore, the amount of phenyltrimethoxysilane added as a refractive index modifier varied in order to control the refractive index of the underlying buffer layer. The refractive index variations and structural changes of these inorganic–organic hybrid films as a function of the processing conditions were analyzed using the prism coupling technique and a Fourier transform infrared spectrometer. We have produced optically transparent films at above 500 nm with a propagation loss of 0.84 and 1.49 dB/cm at 1310 and 1550 nm, respectively.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

A novel sol-gel method for the synthesis of γ-aluminium oxide: development of the sol-gel transformation and characterization of the xerogel

A novel method for the synthesis of aluminium oxide gel has been developed, whereby the sol-gel transformation was investigated. Aluminium tri-sec-butoxide was used as precursor while acetone was chosen as solvent. The synthesis was carried out in a special reactor, which allowed the dosing of steam. ²⁷Al NMR spectroscopy showed that during the sol-gel process the signal at δ∼3 ppm increases strongly corresponding to the formation of hexacoordinated aluminium species. Beside hydrolysis and condensation reactions, the coordination of acetone to a strong Lewis acid aluminium site occurs, which was shown by FTIR and ²⁷Al NMR spectroscopy. Viscosimetric analysis showed that at the beginning of the sol-gel process short polymers are observed while before the gelation a three-dimensional polymer network is formed. After pyrolyzing the gel a high surface area γ-aluminium oxide xerogel was formed. The effect of heating on the morphology and structure was examined by nitrogen physisorption (BET and pore size distribution), XRD and ²⁷Al MAS NMR spectroscopy.     

Comparative study on hydrophobic anti-reflective films from three kinds of methyl-modified silica sols

Methyl-modified silica sols were prepared with the polymer of methyltriethoxysilane (MTES), the polymer of dimethyldiethoxysiloxane (DDS), and hexamethydisizane (HMDS) as mono-, di-, and tri-methyl modifiers respectively. By comparing the size and the shape of clusters in three different methyl-modified silica sols, the special nature of the sol was found to be the key to the property of films. Different modal modification of methyl to silica particles led to different cluster fractal structures that influenced the morphology, the porosity of films and consequently the anti-reflection characteristics. The contribution of methyls in or on clusters directly determined the hydrophobicity. Using mono- or di-methyl-modified silica sol, the film/water contact angles were less than 120°. But it could reach 165° when using tri-methyl-modified silica sol. The lowest reflectivity of film could reach 0.0% for all the three modified sols. As a result of the comparative study, tri-methyl-modified silica sol was more suitable to prepare hydrophobic anti-reflective film with required high optical performance.     

Synthesis and characterization of SiO2-PEG hybrid materials

Sol-gel is a promising technique for the synthesis of organic-inorganic hybrid materials both of class I and II. In materials of class I organic molecules are physically entrapped in an inorganic matrix, while in those of class II organic and inorganic parts are connected by covalent bonds. In this paper a sol-gel procedure to obtain SiO₂-PEG hybrids of class I, in which PEG is simply mixed at the sol stage, is compared to a sol-gel procedure to obtain SiO₂-PEG hybrid materials of class II, where a particular sol-gel Si-C precursor is synthesized. XPS analyses showed the different distribution of the organic phase in the SiO₂ matrix and the bond between PEG and SiO₂ for hybrids of class II. The PEG molecule in hybrid of class II showed an enhanced thermal stability up to 350 °C. Doping with a lithium salt was performed on hybrids of class II, and the ionic conductivity was measured.     

Uniform TiO2 thin films with anatase nanocrystallites synthesized through evaporation-induced assembly

Uniform nanocrystalline anatase (nc-TiO₂) thin films have been synthesized in a ternary copolymer-ethanol–water system through evaporation-induced assembly (EIA) method. The EIA method combines sol–gel and organic–inorganic cooperative assembly technique. The resulting materials were characterized by X-ray diffraction, Fourier transform (FT) Raman spectroscopy, atomic force microscopy, scanning electron microscope, and ellipsometer measurements. The results showed uniform, spherical, and pure anatase crystallites were present in the calcined sample. Moreover, the prepared nc-TiO₂ thin films are smooth and exhibit crack-free nature. A reasonable formation mechanism of uniform nc-TiO₂ thin films is also presented in this work.     

Ordered structure and preferred orientation of boehmite films prepared by the sol-gel method

Several boehmite films were produced using the sol-gel route. The drying process, the film structure evolution and the final texture of the samples were investigated by means of combined X-ray diffraction and weight variation. A remarkable (0 1 0) preferred orientation (about 97% of the crystallites) was found for xerogel films with thickness ranging from 1.5 to 24 μm. The ordered structure is already present in the sol state and is appeared and enhanced during drying, before gelling. This phenomenon may be attributed to the particular boehmite structure that induces special crystallite organization in the aquagel.     

Erbium- and ytterbium-doped sol–gel SiO2–HfO2 crack-free thick films onto silica on silicon substrate

Aware of the difficulties in applying sol–gel technology on the preparation of thin films suitable for optical devices, the present paper reports on the preparation of crack-free erbium- and ytterbium-doped silica: hafnia thick films onto silica on silicon. The film was obtained using a dispersion of silica-hafnia nanoparticles into a binder solution, spin-coating, regular thermal process and rapid thermal process. The used methodology has allowed a significant increase of the film thickness. Based on the presented results good optical-quality films with the required thickness for a fiber matching single mode waveguide were obtained using the erbium- and ytterbium-activated sol–gel silica:hafnia system. The prepared film supports two transversal electric modes at 1550 nm and the difference between the transversal electric mode and the transversal magnetic mode is very small, indicating low birefringence. Photoluminescence of the ⁴I_13/2 → ⁴I_15/2 transition of erbium ions shows a broad band centered at 1.53 μm with full width at a half maximum of 28 nm. Up-conversion emission was carried out under different pump laser powers, and just one transition at red region was observed.     

Synthesis and characterization of chemically cross-linked polyimide-siloxane hybrid films

Chemically cross-linked polyimide and silica hybrid films were prepared through the sol-gel processing. PI matrix was prepared by the reaction of pyromellitic dianhydride with a mixture of diamines e.g., oxydianiline and 2,5-diaminohydroquinon (2,5-DAHQ) to include pendant hydroxyl groups on the chain. These groups were reacted further with isocyanatopropyltriethoxysilane. An appropriate amount of tetraethoxysilane was then added and the sol-gel process was carried out to condense ethoxy groups from both types of silanes thus producing chemically bonded composite films. The films with different silica contents were evaluated by a variety of techniques including FTIR, ²⁹Si NMR, SEM, tensile, thermal, mechanical and thermogravimetric analyses. The chemical interaction between the phases brought about an intimate dispersion of the two phases, which resulted in the formation of nano-sized co-continuous domains. The tensile modulus of such films was higher and thermal expansion coefficient was much lower than those with similar silica contents without inter-phase bonding.     

pH值对溶胶-凝胶法制备的掺铝氧化锌薄膜光电性能的影响

采用溶胶-凝胶法在普通载玻片上制备出c轴择优取向的ZnO: Al(ZAO)透明导电薄膜,研究了溶胶pH值对其结构、表面形貌、电学和光学性能的影响.结果表明:随着pH值的降低晶粒尺寸增大;当溶胶pH值从8.4降低到6.8时,薄膜的电阻率先降低而后略有升高,当pH值为7.2时其电阻率达到最小值2.6×10-3 Ω·cm,进一步分析表明,溶胶pH值的变化影响了薄膜晶界散射,而后者又使载流子迁移率发生了变化;薄膜的透光率在可见光部分随着pH值的降低而升高,而禁带宽度则从3.36 eV降到3.32 eV.