Interfacial sol–gel processing for preparation of porous titania particles using a piezoelectric inkjet nozzle

The aim of the present work is to apply the liquid–liquid interfacial crystallization using a piezoelectric inkjet nozzle to the sol–gel processing. The instillation process was compared with the batch process to elucidate the effectiveness of the inkjet technique on the liquid–liquid interfacial sol–gel processing. The effect of frequency and water concentration in titanium tetraisopoxide (TTIP) solution on titania particle properties was investigated for sol–gel processing with a piezoelectric inkjet nozzle. Titania particles produced by each process were calcined at 500 °C. The crystal structure, morphology, pore size distribution and specific surface area of titania particles were evaluated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption measurement. The photocatalytic activity of titania particles was evaluated by the photodegradation of methylene blue solution under UVC light irradiation.     

Preparation,characterization and photocatalytic activity of a novel nanostructure composite film derived from nanopowder TiO2 and sol–gel process using organic dispersant

A novel sol–gel-derived titanium dioxide nanostructure composite has been prepared by spin-coating and investigated for the purpose of producing films. The processing of the composite sol–gel photocatalysts involved utilizing of precalcinated nanopowder titanium dioxide as filler mixed with sol and heat treated. The sol solution was prepared by adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl 35.5% (mole ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10), then a solution of 2 wt% methylcellulose was added and stirred at room temperature. Precalcinated TiO₂ nanopowder was dispersed in the sol and the prepared mixture was deposited on the microscope glass slide by spin-coating. The inhomogeneity problem in preparation of composite film which causes peeling off and cracking after calcination due to the shrinkage of the films with thermal treatment were overcome by using methylcellulose (MC) as a dispersant. The composite heat treated at approximately 500 °C has the greatest hardness value. Surface morphology of composite deposits by scanning electron microscopy (SEM) showed remarkable increase in the composite surface area. Evaluation of the adhesion and bonding strength between the coating and substrate was carried out by the scratch test technique. The minimum load which caused the complete coating removal, for composite thick film was 200 g/mm² which indicates a strong bond to the substrate. Photocatalytic activity of the composite film was evaluated through the degradation of a textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) as a model pollutant and were compared with those of similar composite thick film without MC, thin film of TiO₂ and TiO₂ nanopowder. The results show that the photocatalytic activity and stability of the composite films are higher than those of nanopowder TiO₂. However, a remarkable increase in the composite surface and good mechanical integrity make this composite film a viable alternative for commercial applications.     

Hydrophilization by coating of silylated polyoxazoline using sol–gel process

Hybrid films prepared from TEOS and polyoxazolines (Si–POx–Si) crosslinking agents were coated on different substrates in order to modify their surface properties. The film cohesion and adhesion on substrates were expected through the hydrogen bonding of the polyoxazoline crosslinked network. Low molecular-weight α,ω-unsaturated polyoxazolines (DA-PMOx)s were synthesized by a one step cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MOx) with a good control over the molecular weight. Based on double thiol-ene coupling (d-TEC) a post-functionalization of DA-PMOx end chains gave in good yield polyoxazoline cross linker (Si–POx–Si). Glass and various polymer substrates (PP, PEI, POM, etc.) were spin coated by the organic–inorganic hybrid films through sol–gel process. AFM, SEM, visible reflectance spectroscopy and contact angle experiments allowed the full characterization of targeted surfaces and demonstrated the efficiency of the polyoxazoline coating.     

Optimization of process parameters using D-optimal design for synthesis of ZnO nanoparticles via sol–gel technique

The experimental conditions for the synthesis of ZnO nanoparticles to produce minimal size were optimized using the D-optimal design. The influence of process parameters involves molar ratio of the starting materials, pH and the calcination temperature on the particle size were evaluated using the polynomial regression. The optimum conditions revealed by the model for obtaining a minimum particle size of ZnO were predicted to have a molar ratio of 1.76, pH of 1.50 and calcination at 402.2 °C. The obtainable particle size upon applying the model is 22.9 nm in compare to experimental result of 18 ± 2 nm was obtained.     

Design of SiO2/ZrO2 core–shell particles using the sol–gel process

Core–shell particles of SiO₂/ZrO₂ were developed using a sol–gel process. Spherical core particles of SiO₂, 320 nm in diameter, were initially prepared using tetraethylorthosilicate (TEOS), and then uniformly shelled with ZrO₂ nano-particles synthesized with zirconium(IV) butoxide (TBOZ). The deposition of ZrO₂ nano-particles on the SiO₂ core particles was generally promoted when increasing the H₂O and TBOZ concentrations and temperature of the sol–gel process. However, micron-sized homo-aggregates of ZrO₂ were formed above certain concentrations of H₂O and TBOZ due to self-aggregation of the nano-ZrO₂ particles. It was very interesting to discover that a chemical bonding between zirconium and silicon bridged by oxygen (Si–O–Zr bond) was developed during the formation of the ZrO₂ shell around the core particles, as the silane groups on the core particles were condensed with zirconium hydroxyl groups during the deposition of ZrO₂. XPS and FT-IR confirmed the chemical bonding of Si–O–Zr in the core–shell particles.     

Fabrication of durable superhydrophobic and superoleophilic cotton fabric with fluorinated silica sol via sol–gel process

Superhydrophobic and superoleophilic cotton fabric was successfully prepared with fluorinated silica sol via a facile sol–gel method. A fluorinated polymeric sol–gel precursor (PHFBMA-MTS) was synthesized via free-radical polymerization by using hexafluorobutyl methacrylate (HFBMA) in the presence of (3-mercaptopropyl)trimethoxysilane (MTS) as the chain transfer agent, which led to the formation of fluoropolymer with alkoxysilane end groups. Then the fluorinated silica sol was prepared by introducing PHFBMA-MTS as the co-precursor of tetraethylorthosilicate (TEOS) in the sol–gel process with ammonium hydroxide as the catalyst, which was then used to fabricate superhydrophobic and superoleophilic fabric coatings through a simple dip-coating method. The coated fabrics showed superhydrophobic property with a high water contact angle of 154.1° and superoleophilic property with an oil contact angle of 0°. Moreover, the coated fabrics still kept superhydrophobicity even after ultrasonic treatment, as well as for organic solutions, acidic solutions. Thus, the coated fabrics were successfully applied to separate oil–water mixture with separation efficiency up to 99.8%. More importantly, the separation efficiency had no significant change after 20 cycles of oil–water separation. These present a simple, low-cost, and durable approach to achieve industrialized application of coated fabrics in oil–water separation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47005.     

Photo-cured epoxy networks reinforced with TiO2 in-situ generated by means of non-hydrolytic sol–gel process

Suspensions of titania nanoparticles in benzyl alcohol were synthesised from TiCl₄ by means of non-hydrolytic sol–gel (NHSG) process. The stable suspensions were mixed with an aliphatic epoxy resin and subsequently photo-polymerised in the presence of a cationic photo-initiator to produce transparent composite films. The presence of titania didn’t influence significantly the polymerisation rate, while a progressive decrease in the maximum value of epoxy groups conversion was observed by increasing the titania content. Gel content analysis demonstrated that all organic species (benzyl alcohol and corresponding by-products) were covalently linked to the epoxy network, suggesting that both ‘active chain end’ and ‘activated monomer’ mechanisms were active during the propagation step in the cationic ring-opening polymerisation. The presence of titania increased significantly both glass transition temperature and modulus (in the rubbery region) confirming the reinforcing and stiffening effect due to both the presence of inorganic nanofillers and, most importantly, a higher cross-linking density of the composite material with respect to the pristine epoxy matrix. Nano-indentation and scratch tests also showed a systematic increase of hardness and scratch resistance by increasing the filler content.     

Fabrication of polyimide/titania nanocomposites containing benzimidazole side groups via sol–gel process

In recent years, polyimide (PI) hybrid materials have received considerable attention owing to the dramatic enhancements over their pristine state in thermal stabilities, mechanical properties and other special features by introducing only a small fraction of inorganic additives. In this investigation, hybrid nanocomposite films of titanium dioxide (TiO₂) in PI were successfully fabricated by an in situ sol–gel process starting from tetraethyl orthotitanate in the solution of poly(amic acid) in N,N-dimethylacetamide. Neat PI was prepared from the polymerization of 2-(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride. The hybrid films were obtained by the hydrolysis–polycondensation of moisture-sensitive titania precursor in poly(amic acid) solution, followed by the elimination of solvents and imidization process. The chelating agent, acetylacetone, was used to reduce the gelation rate of titanium alkoxide. The complete imidization temperature of the poly(amic acid) was delayed; furthermore, the thermal stability of PI was enhanced through the incorporation of the inorganic moieties in the hybrid materials. The chemical and morphological structures of the hybrid materials were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The results show that the TiO₂ particles are well dispersed in the PI matrix with particle size between 15 and 30 nm in diameter.     

Synthesis of nanocrystalline gadolinium doped ceria via sol–gel combustion and sol–gel synthesis routes

Gadolinium doped ceria (GDC) has been investigated as a promising material for application as an electrolyte in intermediate temperature solid oxide fuel cells (IT-SOFC). In this work, 10GDC powders (Gd_0.1Ce_0.9O_1.95) were synthesized by sol–gel combustion and sol–gel synthesis routes using the same complexing agents in both procedures. The thermal behavior of Gd–Ce–O precursor gels was investigated by TG–DSC measurements. X-ray diffraction (XRD) analysis was used for the characterization of phase purity and crystallinity of synthesized samples. Scanning electron microscopy (SEM) was employed for the estimation of surface morphological features. Nitrogen adsorption–desorption (BET model) was used for evaluation of specific surface area. The surface composition was determined by X-ray photoelectron spectroscopy (XPS). Electrical properties of synthesized ceramic samples were studied by means of impedance spectroscopy.     

Preparation of macroporous cordierite monoliths via the sol–gel process accompanied by phase separation

Monolithic cordierite with a cocontinuous macroporous structure has been successfully prepared by the sol–gel process accompanied by phase separation in the presence of poly(acrylamide) (PAAm). Propylene oxide (PO) acts as an acid scavenger to mediate the gelation of MgO–Al₂O₃–SiO₂ ternary system, while PAAm works as a phase-separation inducer as well as a network former. The dried gel and that heat-treated at 800 °C are amorphous, and the sapphirine begins to precipitate at 900 °C, then transforming to orthorhombic β-cordierite at 1100 °C. After heat-treated at and above 1200 °C, the resultant β-cordierite further transforms to stable hexagonal α-cordierite. Heat-treatment changes the macroporous structure of cordierite monoliths such as macropore size and its distribution. The macroporous cordierite monolith after heat-treated at 1200 °C is found to possess a total porosity of 54%, interconnected macropores and dense solid skeletons.     

Effect of Pb excess in sol–gel process on phase composition in PFN ceramics

Lead iron niobate Pb(Fe_0.5Nb_0.5)O₃ (PFN) precursors were prepared using sol–gel synthesis by mixing acetates Pb and Fe with Nb-ethylene glycol–tartarate (Pechini) complex at 80 °C and calcination of gels at 600 °C. Single pyrochlore phase with structure close to Pb₃Nb₄O₁₃ was formed in stoichiometric precursor and Pb₃Nb₄O₁₃ with small amount of perovskite phase Pb(Fe_0.5Nb_0.5)O₃ in nonstoichiometric precursor prepared with the excess of Pb in molar ratio (Pb:Fe:Nb = 1.2:0.5:0.5). Average particle sizes of PFN calcined powders were ～120 nm. The metastable pyrochlore phase was partially decomposed to perovskite phase at sintering temperature of 1150 °C for 2, 4 and 6 h. Excess of Pb caused increasing of the density (7.4 g/cm³) and content of the perovskite phase (～53 vol.%) in ceramics sintered for 4 h. In microstructures of PFN ceramics sintered at 1150 °C for different times, the bimodal grain size distribution was observed with small spherical grains of perovskite phase and larger octahedral grains, which represent the pyrochlore phase. Results of EDX analysis confirm that complex types of pyrochlore phases that differ in iron content were present in ceramics.     

Synthesis and electrochemical properties of LiV3O8 via an improved sol–gel process

LiV₃O₈ cathode material was synthesized via a hydrothermal improved sol–gel process using LiOH, NH₄VO₃ and oxalic acid as raw materials. The thermal decomposition process of the as-prepared LiV₃O₈ precursor was investigated by thermogravimetric (TG) and differential scanning calorimetry (DSC). The structure, morphology and electrochemical performance of the as-synthesized LiV₃O₈ samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM) and the galvanostatic charge–discharge test. The effects of synthesis conditions on phases, structure and electrochemical performance of the LiV₃O₈ samples were particularly discussed. Result shows that pure LiV₃O₈ sample can be obtained at 300 °C, which is much lower than that of normal citric assisted sol–gel method. The sample synthesized at 350 °C exhibits the best electrochemical performance, which can present an initial discharge capacity of 301.1 mAh/g at a current density of 50 mA/g and maintain 271.6 mA/g (about 90.2% of its initial value) after 10 cycles.     

Effect of peptiser species on crystallisation of alumina gel produced by sol–gel process

The present work reports a study on the effect that a peptiser species has on the crystallisation of alumina gel produced by a sol–gel process to help develop a method for producing α-Al₂O₃ at low temperature. The white precipitate of aluminium hydroxide, which was prepared with a homogeneous precipitation method using aluminium nitrate and urea in an aqueous solution, was peptised using various peptisers at room temperature to form a transparent alumina sol. The alumina gel obtained from the alumina sol, which was produced using formic acid as the peptiser, was most dominantly crystallised into α-Al₂O₃ by annealing at 900°C. The optimal [peptiser]/[Al³⁺] (P/A) molar ratio for the crystallisation into α-Al₂O₃ was 0.2. The alumina gel began to crystallise into α-Al₂O₃ with annealing at as low as 500°C when formic acid and a P/A ratio of 0.2 were used.     

Preparation of hierarchically porous spinel CoMn2O4 monoliths via sol–gel process accompanied by phase separation

Cobalt manganite-based hierarchically porous monoliths (HPMs) with three-dimensionally (3D) interconnected macropores and open nanopores have been prepared via the sol–gel process accompanied by phase separation. The controlled hydrolysis and polycondensation of the brominated metal alkoxides, which are generated from an incomplete reaction between epichlorohydrin and MBr₂ (M = Co and Mn) in N,N-dimethylformamide (DMF), form a monolithic gel based on the two divalent metal cations. The dual-polymer strategy using polyvinylpyrrolidone (PVP) and poly(ethylene oxide) (PEO) effectively induces the spinodal decomposition, where PVP and PEO are preferentially distributed to the gel phase and fluid phase, respectively, resulting in a porous gel characterized by the co-continuous structure. The effects of DMF and PVP on the porous morphology derived from the phase separation have been systematically studied. Calcination of the as-dried gels allows for the crystallization into the spinel phase yielding hierarchically porous CoMn₂O₄ monoliths, which have been examined in detail by the structural and compositional analyses.     

Synthesis of TiO2–Ag nanocomposite with sol–gel method and investigation of its antibacterial activity against E. coli

TiO₂–Ag nanocomposite was prepared by the sol–gel method and an azeotropic distillation with benzene was used for dehydration of the gel. Because of gel dehydration by distillation method a nanopowder with a surface area of 230 m²/g was produced which decreased to 80 m²/g after calcination. TEM micrographs and XRD patterns showed that spherical nanosized Ag particles (≈ 10 nm) were deposited among TiO₂ particles. The antibacterial activity of calcined powder at 300 and 500 °C was studied in the presence and in the absence of UV irradiation against Escherichia coli as a model for Gram-negative bacteria. The antibacterial tests confirmed the powder calcined at 300 °C possessed more antibacterial activity than the pure TiO₂, amorphous powder and the powder calcined at 500 °C under UV irradiation. In the absence of UV, the reduction in viable cells was observed only with calcinated powder at 300 °C.     

Enhancement of anticorrosion protection via inhibitor-loaded ZnAlCe-LDH nanocontainers embedded in sol–gel coatings

Inhibitor-loaded ZnAlCe layered double hydroxide (LDH) nanocontainers were prepared through the co-precipitation method. Vanadate and molybdate were used as guest inhibitors intercalating in the interlayer galleries of ZnAlCe-LDHs. The samples were characterized in terms of morphology, structure, and release behavior by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), and inductively coupled plasma (ICP) techniques. To investigate inhibition behavior, the LDHs particles were embedded in a hybrid sol–gel (SiO _x /ZrO _x ) layer on aluminum alloy 2024 measured by electrochemical impedance spectroscopy (EIS). The EIS results show that the sol–gel coating with inhibitor-loaded ZnAlCe-LDH particles exhibits high corrosion resistance due to the active inhibition by the dissolution of ZnAlCe-LDHs and inhibitor anions and the exchange behavior of LDHs. Compared with the addition of ZnAlCe-MoO₄-LDHs, the coating embedded with ZnAlCe-V₂O₇-LDHs exhibited better anticorrosion abilities and provided effective protection after a long immersion time.     

Low-temperature combustion synthesis of nanocrystalline HoFeO3 powders via a sol–gel method using glycin

Single phase nanocrystalline HoFeO₃ powders were successfully synthesized by the sol–gel self-propagation combustion method using glycin (C₂H₅NO₂) as the chelating reagent at a low combustion temperature. Four different mole ratios of glycin to metal nitrate (G/M) were used to prepare HoFeO₃ powders in the experiment. The XRD patterns indicate monophasic HoFeO₃ powders can be formed by further calcination, the SEM micrographs show that the nano-sized grains with distinguishable boundaries had been obtained. The M–H curves show HoFeO₃ powders had the characteristic of antiferromagnetism at 50 K, while the powders had the characteristic of paramagnetism as the ambient temperature reached 100 K or 300 K. The FC/ZFC magnetic measurement results demonstrate that there was a transition from antiferromagnetism to paramagnetism in HoFeO₃ nanopowders as the temperature was increased.     

Facile preparation of well-defined macroporous yttria-stabilized zirconia monoliths via sol–gel process accompanied by phase separation

Yttria-stabilized zirconia monoliths with well-defined macropores and high porosity have been successfully fabricated via sol–gel process accompanied by phase separation. Propylene oxide acts as an acid consumer to mediate sol–gel process, and poly (ethylene oxide) is used to induce phase separation. Ethylene glycol is applied as chelating agent, and formamide serves as drying control chemical additive to inhibit cracking during drying stage. Proper proportion of the starting compositions allows the generation of well-defined macroporous YSZ monoliths with co-continuous skeletons and porosity as high as more than 60 %. The dried gels are amorphous and crystalline of ZrO₂ precipitates after heat treatment between 400 and 1200 °C without formation of monoclinic ZrO₂, which indicating a wide application prospects.     

Anatase–rutile transformation of TiO2 sol–gel coatings deposited on different substrates

Titanium dioxide is widely used in a lot of applications. The properties of TiO₂ strongly depend on its phase composition. The transformation temperature between phases is influenced by a lot of factors. One of them is a type of substrate under the TiO₂ film. In presented work, thin films of TiO₂ were deposited by the sol–gel method on silicon, stainless steel (304 L) and Co–Cr–Mo alloy (Vitallium). The process of anatase–rutile phase transformation was investigated by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) studies of deposited coatings. The results were compared with anatase–rutile transformations temperature of TiO₂ powders obtained by analogous sol–gel process. The temperature of anatase–rutile phase transformation changed in the range of 700–1000 °C and strongly depends on a kind of substrate. It was found that anatase–rutile transformation of TiO₂ coating proceeded at a higher temperature than rutilization of titania powders.