Effect of solution pH on the surface morphology of sol–gel derived silica gel

We have examined the effect of solution acidity on the textural characteristics of silica gels prepared by sol–gel synthesis using tetraethyl orthosilicate (TEOS) as a silica precursor and cetyltrimethylammonium bromide (CTAB) as a template. Using IR spectroscopy, we have studied micellar TEOS solutions and the synthesized silica gel samples. The results demonstrate that, in an alkaline medium in a water–ethanol solution, SiO₂ experiences short-range ordering on the surface of micelles formed by CTAB molecules, whereas in an acid medium the process is not influenced by the presence of CTAB. Nitrogen porosimetry and electron microscopy data indicate that the silica gel obtained at pH 2 is microporous, with an average pore size of 2 nm. In an alkaline medium at pH 10, we obtained mesoporous SiO₂ (18 nm) with a narrow pore size distribution and a specific surface area of 110 m²/g.     

Effect of the Brij 30 porogen on the properties of sol–gel derived thin polymethylsilsesquioxane films

Thin polymethylsilsesquioxane films with Brij 30 porogen concentrations in the range ω_surf = 15.5–52.5 wt % have been produced by a sol–gel process. Their dielectric permittivity, refractive index, relative porosity, and shrinkage have been measured as functions of heat treatment temperature and porogen concentration.     

Effect of water content in sol on optical properties of hybrid sol–gel derived TiO2/SiO2/ormosil film

Sol–gel derived TiO₂/SiO₂/ormosil hybrid planar waveguides have been deposited on soda-lime glass slides and silicon substrates, films were heat treated at 150 °C for 2 h or dried at room temperature. Different amounts of water were added to sols to study their impacts on microstructures and optical properties of films. The samples were characterized by m-line spectroscopy, Fourier transform infrared spectroscopy (FT-IR), UV/VIS/NIR spectrophotometer (UV–vis), atomic force microscopy (AFM), thermal analysis instrument and scattering-detection method. The refractive index was found to have the largest value at the molar ratio H₂O/OR = 1 in sol (OR means OCH₃, OC₂H₅ and OC₄H₉ in the sol), whereas the thickest film appears at H₂O/OR = 1/2. The rms surface roughness of all the films is lower than 1.1 nm, and increases with the increase of water content in sol. Higher water content leads to higher attenuation of film.     

Effect of solvents on the preparation of lithium aluminate by sol–gel method

γ-Lithium aluminate was prepared by sol–gel method using lithium methoxide and aluminum-sec-butoxide precursors in i-propanol, n- and tert-butanol. Clear gels could be obtained due to the addition of ethylacetoacetate and the dried solids were calcined at 550 and 900 °C. The resulting solids were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermo-gravimetric analysis/differential thermal analysis (TGA/DTA). γ-Lithium aluminate with the highest purity was obtained with t-butanol solvent and LiAl₅O₈ was the second major phase.     

Effect of annealing temperature on electrical and nano-structural properties of sol–gel derived ZnO thin films

Zinc oxide (ZnO) thin films have been prepared on silicon substrates by sol–gel spin coating technique with spinning speed of 3,000 rpm. The films were annealed at different temperatures from 200 to 500 °C and found that ZnO films exhibit different nanostructures at different annealing temperatures. The X-ray diffraction (XRD) results showed that the ZnO films convert from amorphous to polycrystalline phase after annealing at 400 °C. The metal oxide semiconductor (MOS) capacitors were fabricated using ZnO films deposited on pre-cleaned silicon (100) substrates and electrical properties such as current versus voltage (I–V) and capacitance versus voltage (C–V) characteristics were studied. The electrical resistivity decreased with increasing annealing temperature. The oxide capacitance was measured at different annealing temperatures and different signal frequencies. The dielectric constant and the loss factor (tanδ) were increased with increase of annealing temperature.     

Effect of Ni doping on the microstructure and high Curie temperature ferromagnetism in sol–gel derived titania powders

Undoped, 0.05 and 0.5 mol% Ni-doped TiO₂ powders were prepared by a modified sol–gel route. The doping effects on the microstructure and magnetism for the powdered samples have been systematically investigated. Doping of Ni in TiO₂ inhibited rutile crystal growth. The probable reason for this is discussed on the basis of band calculation based analysis of electronic structures of 3d transition metal-doped TiO₂ and the energetic, transformation kinetics and phase stability of anatase over rutile as the function of particle size. Room temperature ferromagnetism (RTFM) with the saturation magnetization of 12 m emu g⁻¹ and Curie temperature as high as 820 K is observed only in case of 0.05 mol% Ni:TiO₂ powdered sample, whereas undoped TiO₂ was diamagnetic and 0.5 mol% Ni:TiO₂ was paramagnetic in nature. The role of any magnetic impurity or any Ni metal in the origin of the RTFM has been ruled out by energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and high resolution TEM (HRTEM) analysis, whereas magnetic force microscopy (MFM) established the presence of magnetic domains, supporting the intrinsic diluted magnetic semiconductor behavior. The observed ferromagnetism has been attributed to the spin ordering through exchange interaction between holes trapped in oxygen orbitals adjacent to Ni substitutional sites.     

Effects of Mg doping on sol–gel derived nanocrystalline hydroxyapatite thin films

Abstract

Both pure and Mg doped thin films were fabricated by sol–gel dip coating. The films were sintered either at 800 or 1000°C. The average grain size of the films was significantly affected by Mg substitution in the hydroxyapatite (HA) structure and change in the sintering temperature. The grains were considerably larger in the films sintered at higher temperatures. In addition, Mg doped films contained significantly larger grains compared to undoped HA films. Mg doping also caused rodlike grains at 800°C, and led to whitlockite (β-TCP) formation at 1000°C. The ratio of the existing phases was estimated as β-TCP/HA=27 : 73. All the films had rough surfaces with high porosity. It was also observed that undoped films had higher surface roughness than Mg doped ones.     

Investigations on the optical properties of sol–gel derived lanthanum doped lead titanate thin films

In the present work we studied the optical properties of undoped and La doped lead titanate thin films, and also demonstrated that the optical characterization of thin films can be used as an effective diagnostic tool to assess film quality. The optical properties of Pb_1−xLa_xTi_1−x/4O₃ [where x=0 (undoped), 10, 15, 20, 25 and 30 at.%] thin films were investigated using both transmission and reflection spectra in the 200–900-nm wavelength range. The refractive index (n), extinction coefficient (k) and the thickness of the film (d_f) were determined from the measured transmission spectra. The thickness of the film obtained from the interference fringes in transmission or reflection spectra matched well with those obtained from other methods. The appearance of interference fringes is an indication of the thickness uniformity of the film. The low value of extinction coefficient (in the order of 10⁻²) as observed in our films is a qualitative indication of excellent surface smoothness of the films. The densities of the films were estimated from their refractive indices using effective medium approximation. The average oscillator strength and its associated wavelength were estimated using a Sellmeier-type dispersion equation. Absorption coefficient (α) and the band-gap energy (E_g) were obtained for undoped and La doped films with varying La concentration. It was found that the refractive index and packing fraction values decrease with La doping. La doping was found to decrease the grain size of the films and increase the density of individual grains. Increased La content led to clustering of smaller grains. The observed variation of band-gap energy with La doping has been correlated to the observed microstructure of these films.     

Fire retardancy of sol–gel derived titania wood-inorganic composites

Sol–gel technology was applied in tailoring novel wood-made-inorganic composites with improved thermal and fire properties. In practice, composites materials were prepared by impregnating pine sapwood wood with nano-scaled precursor solutions derived from titanium(IV) isopropoxide followed by a thermal curing process. Thermal and fire properties were evaluated by thermal analysis and cone calorimetry, whereas flammability was specified by oxygen index (LOI) and UL 94 test. Peak heat release rates were moderately reduced indicating fire retardance potential in terms of flame spread attributed to the appropriate protection layer action of the titania-based depositions. LOI (oxygen index) values of these composites were increased up to 38 vol.% in comparison to 23 vol.% for untreated wood. The flame retardancy performance depends on the fire scenario and is strongly influenced by wood loading and crack-free deposition of the titania layers inside the composite.     

Solvent effect on the sol–gel synthesis of lithium aluminate

Lithium aluminate was prepared from different alcohols as solvents. Aluminum sec-butoxide was dissolved with ethyl, isopropyl or n-butyl alcohol and hydrolyzed simultaneously with LiOH. The resulting solids were characterized by XRD, DTA, TGA and SEM. Lithium aluminates were also prepared by fusion and peroxide methods as comparison in thermal behavior. It was found that the precursors are semi-cristalline Al-Li mixed carbonates if ethyl or isopropyl alcohol was used, whereas a highly cristalline Al–Li hydroxyl was obtained with the n-butyl alcohol. In the ethyl and isopropyl calcined preparations (800°C), the carbonates were partially eliminated, while the highest yield of γ-LiAlO₂ phase was obtained in the n-butyl sample.     

Synthesis and thermomechanical characterization of polyimides reinforced with the sol–gel derived nanoparticles

Polyimide-based nanocomposites prepared by the in situ generation of inorganic nanoparticles (silica) through the sol–gel process were characterized by kinetics of water uptake, ther mogravimetry and dynamic mechanical analysis.

Silica particles turned out to possess a rather loose inner structure characterized by enhanced water diffusivities andby dynamic elasticity moduli comparable to that of the pristine, glassy PI. Thermal stability and thermomechanical properties of nano composites in the glassy state remained nearly the same as those of the pristine PI, while a significant reinforcement effect was observed for the rubbery PI matrix.     

Synthesis and thermomechanical characterization of polyimides reinforced with the sol–gel derived nanoparticles

Polyimide-based nanocomposites prepared by the in situ generation of inorganic nanoparticles (silica) through the sol–gel process were characterized by kinetics of water uptake, thermogravimetry and dynamic mechanical analysis.Silica particles turned out to possess a rather loose inner structure characterized by enhanced water diffusivities and by dynamic elasticity moduli comparable to that of the pristine, glassy PI. Thermal stability and thermomechanical properties of nanocomposites in the glassy state remained nearly the same as those of the pristine PI, while a significant reinforcement effect was observed for the rubbery PI matrix.     

Influence of platinum nano-particles on the photocatalytic activity of sol–gel derived TiO2 films

Different 1-step or 2-step photo-platinization methods have been implemented to load sol–gel TiO₂ photocatalytic thin films with platinum nano-particles. These methods enable flexible variations in the amount of loaded particles, and they strongly influence the structure and size of these particles and the morphology of derived platinized films. The photocatalytic activity of platinized films has been studied. It is shown that optimal platinization conditions allow envisaging thin film photocatalysts with enhanced properties. Best performances are reached when the films are loaded with platinum particles for 30 or 60 min using a 1-step platinization method, which yields photocatalytic activities about 4 times greater than that of non-platinized films. Photocatalytic activity differences induced by the 1-step or 2-step photo-platinization methods are discussed in relation to the amount of loaded platinum together with structural and morphological features.     

Vibrational spectroscopic studies on crystallisation of sol–gel derived thin films of calcia–alumina binary compound

An optimized sol–gel process has been developed to produce homogeneous thin films of calcium aluminate binary (12CaO·7Al₂O₃) compound, on magnesium oxide substrates via spin coating. Fourier transform infrared and Raman spectroscopies have been employed to investigate the effect of annealing temperature and duration on the phase transformations in the films. Heat treatment at 1,300 °C under air atmosphere for 2 h produced single-phase 12CaO·7Al₂O₃ films. However, annealing at a lower temperature of 1,100 °C in air for a period of 4 h in total resulted in the crystallization of 5CaO·3Al₂O₃ rather than 12CaO·7Al₂O₃. The X-ray photoelectron spectrum of the thin film annealed at 1,300 °C corresponds to the binding energies of C12A7 compound. The annealing temperature of 1,300 °C for 2 h is found to be sufficient for formulating single phase calcia–alumina binary films in correct stoichiometric ratio of 12:7.     

Investigations on the photocatalytic activity of sol–gel derived plain and Fe/Nb-doped titania coatings on glass substrates

Plain and doped (Fe³⁺ and Nb⁵⁺) titania coatings were deposited by dip coating on soda lime glass substrates using titania sol synthesized by sol–gel route in combination with commercial nanoparticle dispersions. The dopant concentrations were fixed at 0.07 wt% and the coatings heat treated at 400 °C were characterized with respect to their thickness, phase composition, hydrophilicity/hydrophobicity and microstructure. Photocatalytic activity testing was carried out on the coatings by following up the degradation of methylene blue dye for up to 4 h at 1 h time intervals after exposure to sunlight. The effect of a trivalent and pentavalent doping of Ti⁴⁺ sites on photocatalytic activity of TiO₂ was investigated.     

Influence of annealing temperature on the structural,topographical and optical properties of sol–gel derived ZnO thin films

This investigation deals with the effect of annealing temperature on the structural, topographical and optical properties of Zinc Oxide thin films prepared by sol–gel method. The structural properties were studied using X-ray diffraction and the recorded patterns indicated that all the films had a preferred orientation along (002) plane and the crystallinity along with the grain size were augmented with annealing temperature. The topographical modification of the films due to heat treatment was probed by atomic force microscopy which revealed that annealing roughened the surface of the film. The optical properties were examined by a UV–visible spectrophotometer which exhibited that maximum transmittance reached nearly 90% and it diminished with increasing annealing temperature.     

Effect of hydrolysis on the phase evolution of water-based sol–gel hydroxyapatite and its application to bioactive coatings

In a previous report, we demonstrated a successful synthesis of crystalline hydroxyapatite (HA) through the use of a water-based sol–gel process. It was shown that the apatite can be obtained at temperatures generally below 400 °C, providing a great advantage for practical bioactive coating purposes. The influence of hydrolysis of phosphorus sol solution on the phase evolution of the resulting HA is the focus of this investigation. Experimental results show that, in the absence of acid catalyst, a long-term hydrolysis, i.e. >4 h, is required for better evolution of apatitic phase. Such a phase evolution is mainly attributed to an increased concentration of apatitic phase, rather than improved crystallinity in the calcined gels. With the aid of acid catalyst, we found that a well-crystalline HA can be synthesized over a time period shorter by 2–3 orders of magnitude than those without catalyst, i.e. a few minutes. In almost all cases, a small amount of tricalcium phosphate (TCP) was detected, which may be explainable by the formation of oligomeric derivatives of the phosphorus sol during synthesis, where calcium phosphate derivatives with lower Ca/P ratio than stoichiometry can be developed. By selecting an optimal sol as a dipping source, highly-porous dental root specimens were coated and a thin, dense, adhesive (upon finger-nail scratching test) coating was achieved after calcinations at 375 °C. An in vitro test also shows a bioactive character of the coating.     

Effect of gas enhanced metal-semiconductor-metal UV photodetectors based on thermal annealing tungsten oxide thin film prepared by sol–gel method

Metal-semiconductor-metal ultraviolet photodetectors were fabricated on annealed tungsten oxide thin films which were synthesized by the sol–gel reaction. Surface morphology, microstructure, opto-electrical properties and crystal structure tests of the W₁₈O₄₉ thin films were examined by scanning electron microscopy, transmission, photoluminescence, and X-ray diffraction, respectively. The photo-responsivity of the photodetector shows a dependence on atmosphere environments. The photocurrent measured in a vacuum is about ~2 times higher than the illuminated photocurrent in air. The illumination conductance in a vacuum and in air increase by a factor of 100 compared to that in oxygen ambient. Furthermore, the obtained photoresponse curves showed significant changes in dark, under illumination, and during recovery for gas switching experiment. The solid-state process of electron-hole generation/recombination and surface effects of oxygen was discussed to explain the changes in the observed photoresponse.     

Adsorptive properties of sol–gel derived hybrid organic/inorganic coatings

Hybrid organic-inorganic sol–gel derived coatings have been prepared by dip coating on glass substrates from alcoholic solutions of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), 3-aminopropyltriethoxysilane (APTES), 3-glycidoxypropyltrimethoxysilane (GPTMS) and phenyltriethoxysilane (PhTES). The hybrid materials have been fully characterized by means of solid state NMR spectroscopy and X-ray diffraction. The degree of cross-linking and the extent of interaction between silica and silsesquioxane phases appear dependent on the ratio between TEOS and organotrialkoxysilane and on the chemical features of the organic function linked to silicon, and influence the sorption ability towards aromatic compounds of hybrid films. The hybrid coatings have been put into an optical-grade quartz chamber placed into a UV–VIS–NIR spectrophotometer and the organic compounds have been allowed flowing through the chamber recording of molecule absorption spectra vs. time. Absorbance curves vs. time have also been collected at a fixed wavelength for different molecule-coating couples and simple kinetic models have been used for comparing the adsorption capability of the different films, which has been related to the chemical interactions between molecules and coatings.     

The effect of acid mixture on the structure of sol–gel PZT fibers

Author's previous studies [J. Am. Ceram. Soc., in press] showed that the acidification of the precursor solution controls the strength and length of sol–gel PZT fibers. Two acids, acetic acid (CH₃COOH) and methacrylic acid (C₄H₆O₂), were studied. C₄H₆O₂ produced longer fibers with small cracks, while CH₃COOH produced shorter and denser fibers. In order to take advantage of the opposite effect of each of these acids, mixtures of acetic and methacrylic acid are used in this work to obtain longer and dense fibers. The effect of the ratio of CH₃COOH/C₄H₆O₂ mixture on the precursors' chemical structure, crystalline phase formation and microstructure of PZT fibers is investigated and discussed. Long and almost crack-free PZT fibers are obtained for a 1/2 ratio of CH₃COOH/C₄H₆O₂.