Observations on chromate conversion coatings from a sol–gel perspective

Chromate conversion coatings (CCCs) have been applied to aluminum substrates for many years to improve corrosion resistance and paint adhesion. In recent years the so-called sol–gel chemistry based coating systems have been examined as possible replacements for CCCs on aluminum. A mechanism is proposed for the formation of CCC on aluminum that is consistent with sol–gel chemistry principles. The conclusions illustrate important considerations for developing non-CCCs for aluminum.     

Polymeric sol–gel coatings as protective layers of aluminium alloys

Sol–gel route is an emerging technology to synthesize coatings of a wide variety of properties taylored. In this work three low temperature cured coatings has been studied to evaluate their protective properties in order to be used as protective barrier coatings for aluminium alloys with potential architectural and automotive applications. These three coatings are novel modified silane nanocomposites coatings obtained mixing two sols separately prepared: a pre-hydrolysed 3-glycidyloxypropyl trimethoxysilane (GPTS) with acidic catalyst and another obtained from tetraethylorthosilicate/methyltriethoxysilane (TEOS/MTES). Particulated coatings were obtained by addition of 25 wt.% particles of Aerosil 300 and Aerosil R972, respectively. The protective properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) which showed notably differences among them not only from the protective viewpoint but the hydrophobic nature of the coatings and the controlling corrosion mechanism in each case.     

Improvement of microstructure property of low dielectric constant nanoporous SiOF thin films prepared by sol–gel method

Using hydrofluoric acid (HF) as acid catalyst, F doped nanoporous low-k SiO₂ thin films were prepared through sol–gel method. Compared with the hydrochloric acid (HCl) catalyzed film, the films showed better micro-structural and dielectric properties. The improvements were investigated by high-resolution scanning electron microscopy (HR-SEM), Fourier transform infrared spectroscopy (FTIR), and capacitance–voltage (C–V) and current–voltage (I–V) techniques. The results of N₂ adsorption/desorption further confirmed the HR-SEM morphologies and indicated that the suited introduction of HF increased the porosity and decreased the pore size distribution (about 10 nm). The incorporation of HF effectively adjusts the microstructures and the chemical bonds, and thus significantly improves the dielectric properties of the films; the dielectric constant was reduced to 1.5.     

Transparent UV curable antistatic hybrid coatings on polycarbonate prepared by the sol–gel method

UV curable, hard, and transparent organic–inorganic hybrid coatings with covalent links between the inorganic and the organic networks were prepared by the sol–gel method. These hybrid coating materials were synthesised using a commercially available, acrylate end-capped polyurethane oligomeric resin, hexanedioldiacrylate (HDDA) as a reactive solvent, 3-(trimethoxysilyl)propoxymethacrylate (MPTMS) as a coupling agent between the organic and inorganic phase, and a metal alkoxide, tetraethylorthosilicate (TEOS). The materials were applied onto polycarbonate sheets and UV cured, followed by a thermal treatment to give a transparent coating with a good adhesion and abrasion resistance. The high transmission and the thermogravimetric behaviour indicate the presence of a nanoscale hybrid composition. In a taber abrasion test, uncoated polycarbonate sheets exhibit a 48% decrease in light transmittance at 633 nm after 300 wear cycles, whereas the hybrid coating system containing 10 wt% silica shows only 10% decrease in light transmittance. For obtaining antistatic coatings, an intrinsically conductive polymer (ICP) was added to the optimised coating formulation. It is shown that the surface resistivity of the organic–inorganic hybrid coating can be reduced from 10¹⁶ to 10⁶ Ω for a high concentration of ICP in the coating formulation.     

Ti-modified alumina supports prepared by sol–gel method used for deep HDS catalysts

The typical physico-chemical properties and their hydrodesulfurization activities of NiMo/TiO₂-Al₂O₃ series catalysts with different TiO₂ loadings were studied. The catalysts were evaluated with a blend of two kinds of commercially available diesels in a micro-reactor unit. Many techniques including N₂-adsorption, UV–vis DRS, XRD, FT-Raman, TPR, pyridine FT-IR and DRIFT were used to characterize the surface and structural properties of TiO₂-Al₂O₃ binary oxide supports and the NiMo/TiO₂-Al₂O₃ catalysts. The samples prepared by sol–gel method possessed large specific surface areas, pore volumes and large average pore sizes that were suitable for the high dispersion of nickel and molybdenum active components. UV–vis DRS, XRD and FT-Raman results indicated that the presence of anatase TiO₂ species facilitated the formation of coordinatively unsaturated sites (CUS) or sulfur vacancies, and also promoted high dispersion of Mo active phase on the catalyst surfaces. DRIFT spectra of NO adsorbed on the pure MoS₂ and the catalysts with TiO₂ loadings of 15 and 30% showed that NiMo/TiO₂-Al₂O₃ catalysts possessed more CUS than that of pure MoS₂. HDS efficiencies and the above characterization results confirmed that the incorporation of TiO₂ into Al₂O₃ could adjust the interaction between support and active metals, enhanced the reducibility of molybdenum and thus resulted in the high activity of HDS reaction.     

Preparation and characterization of sol–gel derived mesoporous titania spheroids

The formation of mesoporous spherical titania particles via hydrolysis of pure titanium tetra-isopropoxide in n-heptane solution upon the application of a slow stirring rate is described. Calcination of the dry hydrolysis product produced pure anatase at 400–600°C, and rutile at 800°C. Nitrogen adsorption results indicate high surface area (S_BET 132 m²/g) and uniform mesopores peaking at 10 nm for the material calcined at 400°C. Upon calcination at 600°C, the pore size remained at 10 nm, whereas the S_BET value was decreased. The material calcined at 400°C was found by scanning electron microcopy to be shaped into spherical particles about 2 μm in diameter. Sizes of the spherical particles were unchanged at 400°C and up to 800°C. This was ascribed to the spherical morphology of the particles which prevented primary particles from growing beyond the boundary of the host aggregate even when the rutile phase transition occurred at 800°C.     

Fischer–Tropsch synthesis over Co–SiO2 catalysts prepared by the sol–gel method

Fischer–Tropsch synthesis was carried out in slurry phase over uniformly dispersed Co–SiO₂ catalysts prepared by the sol–gel method. When 0.01–1 wt.% of noble metals were added to the Co–SiO₂ catalysts, a high and stable catalytic activity was obtained over 60 h of the reaction at 503 K and 1 MPa. The addition of noble metals increased the reducibility of surface Co on the catalysts, without changing the particle size of Co metal significantly. High dispersion of metallic Co species stabilized on SiO₂ was responsible for stable activity. The uniform pore size of the catalysts was enlarged by varying the preparation conditions and by adding organic compounds such as N,N-dimethylformamide and formamide. Increased pore size resulted in decrease in CO conversion and selectivity for CO₂, a byproduct, and an increase in the olefin/paraffin ratio of the products. By modifying the surface of wide pore silica with Co–SiO₂ prepared by the sol–gel method, a bimodal pore structured catalyst was prepared. The bimodal catalyst showed high catalytic performance with reducing the amount of the expensive sol–gel Co–SiO₂.     

Effect of pH in a sol–gel synthesis on the physicochemical properties of Pd–alumina three-way catalyst

The effect of pH during sol–gel synthesis on the structural and physicochemical properties of a Pd–Al₂O₃ three-way catalyst (TWC) prepared by the sol–gel method was investigated by using BET, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and solid state ²⁷Al MAS NMR. The Pd–Al₂O₃ catalyst prepared at pH=10 (Pd–Al₂O₃–B) showed a high activity in three-way catalytic reaction, a high dispersion of Pd, and large surface area and pore volume. A basic condition (pH=10) in the sol–gel process was essential for the preparation of highly dispersed palladium clusters on alumina gel. The formation of highly stable palladium oxide species in Pd–Al₂O₃–B that were not completely reduced at 423 K was ascribed to the strong interaction between Pd and oxygen in alumina texture, resulting in the formation of –Al–O–Pd bond.     

Sensitive glasslike sol–gel materials suitable for environmental light sensors

New sol–gel based sensitive materials able to detect moderate doses of UV, Vis and near IR radiations have been designed, prepared and characterised. These glasslike detectors are respectively composed by four different sols of inorganic and hybrid organic–inorganic silica matrixes. The sols were prepared from alkoxide (TEOS) and alkylalkoxide (GLYMO) precursors with molar ratios 1:0, 1:1, 1:4 and 0:1, respectively. All the sols were doped with an organic photochromic dye (spiropyran). The detectors characterisation was carried out by means of exposures to natural light under different light intensities (100–3000 lx). The highest sensitivity against the light radiation was found for sols with molar ratio TEOS:GLYMO of 1:1. The time response of detectors is found at about 10 min and their life time is roughly 4 months at least. Moreover, the detectors show good optical reversibility. These sensitive glasslike materials have been designed to be applied for preservation of historical goods. They can detect and evaluate dangerous light doses for the proper conservation conditions of historical materials, which are sensitive or moderately sensitive against light radiation (<600 lx).     

Effect of solvo-thermal treatment temperature on the properties of sol–gel ZrO2–TiO2 mixed oxides as HDS catalyst supports

ZrO₂–TiO₂ mixed oxide (30–70 mol/mol) was prepared by low-temperature sol–gel followed by solvo-thermal treatment (1 day) at various temperatures (40, 80, 120, 160 and 200 °C). Selected samples of the corresponding single oxides were also prepared. Materials characterization was carried out by N₂ physisorption, XRD, thermal analysis (TG-DTA) and UV–vis DRS, infra-red and Laser-Raman spectroscopies. Binary solids of enhanced pore volume and pore size diameter were obtained by increasing the post-treatment severity. Anatase TiO₂ micro-segregation was evidenced by Raman spectroscopy for the mixed oxide solvo-treated at the highest temperature. This solid also showed the highest crystallization temperature to ZrTiO₄ (702 °C). Mo impregnated (2.8 atom nm⁻²) on various mixed oxides was sulfided under H₂S/H₂ (400 °C, 1 h), the catalysts being tested in the dibenzothiophene hydrodesulfurization (HDS, T = 320 °C, P = 5.59 MPa). By increasing the severity of the solvo-treatment improved supports for MoS₂ phase were obtained. The HDS activity of the catalyst with carrier post-treated at 200 °C was 40% higher (in per total mass basis) than that of sulfided Mo supported on the binary oxide solvo-treated at 80 °C. The ZrO₂–TiO₂-supported catalysts showed higher selectivity to products from the hydrogenation route than their counterparts supported on either single oxide.     

Electrical conductivity of sol–gel derived yttria-stabilized zirconia

A 3 mol% Y₂O₃ zirconia stabilized powder has been synthesized by destabilization of an aqueous zirconia sol prepared by the alkoxide hydrolysis method. The powder calcined at 500°C is ultrafine with tetragonal crystallites of about 8 nm, slightly agglomerated and with a narrow pore size distribution having an average pore size of 5.2 nm. Zirconia ceramics with density higher than 92%TD and grain size on the order of 100 nm have been obtained by uniaxial pressing at 500 MPa and vacuum sintering at 1000°C. Electrical conductivity of sintered samples, evaluated by complex impedance spectroscopy measurements, indicated that the zirconia stabilized with 3 mol% Y₂O₃ can potentially be used as an oxygen semipermeable dense membrane, but only at a relatively high temperature.     

Investigation of the sol–gel transition of electrochemically prepared acrylamide bisacrylamide gels

A novel technique based on the chronoamperometric measurements was developed to study the sol–gel transition for the solution free radical cross-linking co-polymerization of acrylamide and N, N′-methylene bisacrylamide. The gels were synthesized electrochemically at room temperature in the presence of an initiator, ammonium persulfate. No chemical activator was used for accelerating the reaction; instead a direct voltage was applied by means of a silver-working electrode placed in the reaction mixture. It is found that the current measured during the gelation process monitors the change in the concentration of radicals, which are free to move in the reacting sample. The current due to these free radicals measures the weight average degree of polymerization and gel fraction around the gel point. Observations around the gel point, for low polymerization voltages, show that the gel fraction exponent β and the weight average degree of polymerization exponent γ agree with the mean-field results for low acrylamide concentrations. The samples synthesized above a certain voltage do not show self-similarity at the critical point. This is due to the increase in the local density, so does the heterogeneity, of the gel around the silver electrode, therefore, they do not obey the scaling behavior near the critical point.     

Enhanced photoactivity of silica-embedded titania particles prepared by sol–gel process for the decomposition of trichloroethylene

Silica-embedded titania photocatalyst (X-silica/titania, X denotes at.% of silicon) of improved photoactivity was prepared by the sol–gel technique. The photoactivity of the X-silica/titania particles was increased by increasing the silica content and reached a maximum. The highest photoactivity was obtained when silica content was 30% and five times higher than that of Degussa P25. The embedding of amorphous silica into nanophase titania matrix helped to increase the thermal stability of titania which suppressed the formation of anatase into rutile and made it possible to calcine the silica/titania particles at higher calcination temperature. This high temperature heat treatment resulted in the high crystallinity of the silica/titania particles. Surface area of X-silica/titania particles was monotonically increased by increasing the silica content. The average pore size and pore volume, however, has a maximum at 30%, at which mesopores larger than 30 nm were observed. Therefore, we concluded that the large pore size and pore volume were responsible for the optimum composition of silica to titania. The enhanced photoactivity of silica-embedded titania particles was achieved by simultaneously increasing both the surface area and the crystallinity through embedding amorphous silica into titania.     

Characteristics of the Pd-only three-way catalysts prepared by sol–gel method

Pd-only three-way catalysts prepared by the sol–gel method were investigated by the three-way catalytic performance test with a simulated exhaust gas in a continuous U-tube quartz reactor at a gas hourly space velocity of 72 000 h⁻¹. The catalysts were characterized with XRD, XPS, BET surface area and pore volume. The activity and thermal stability of the Pd–Al₂O₃ catalyst prepared at pH 10 were superior to those at pH 4 during hydrolysis and condensation, which could be explained by the anchoring effect. Zr and V were found to be good promoters for the enhancement of the thermal stability and SO₂ resistance, respectively. Optimally formulated catalyst, Pd(1)–V(2)–Zr(10)–Al₂O₃, was thermally stable up to 900^oC and showed a much more improved low-temperature activity and excellent SO₂ resistance.     

Oxidative carbonylation of phenol over the mesoporous palladium-copper-oxide/silica catalyst prepared by sol–gel coupling with W/O microemulsion

A novel mesoporous catalyst Pd-Cu-O/SiO₂ were prepared by sol–gel method coupling with W/O microemulsion for oxidative carbonylation of phenol to diphenyl carbonate (DPC). It has larger specific surface area, pore volume and rather narrow pore size distribution in the range of mesopore. The catalyst shows a comparatively good activity for the synthesis of DPC and the yield reaches to 20.3%, the turnover frequency (TOF) is 15.1 mol-DPC/mol-Pd h, at certain conditions. The less dispersed active centers and the diffusion resistance caused by the numerous pores influence the reaction negatively.     

Preparation and characterization of mesostructured polymer-functionalized sol–gel-derived thin films

The present study attempts to incorporate methacrylate-based polymers into ordered lamellar organic/inorganic nanocomposite films composed of alternating SiO₂/polymer layers. The films are prepared by dip-coating from a solution containing the monomers and silica precursors, thus leading to composite lamellar mesostructured materials through evaporation-induced self-assembly (EISA). A polymerizable coupling agent is added to covalently link the polymers to the silica matrix. The final polymer/SiO₂ hybrid material is obtained by a separate free-radical polymerization step, initiated by UV exposure or thermal treatment. Using trimethoxy(7-octen-1-yl)silane as a coupling agent, a procedure was established that preserved the mesostructure and maintained the swelling properties of the polymers, while acrylate-based coupling agents lead to a significant distortion of the film mesostructure. Structure and composition of the films were studied by X-ray diffraction, NMR and IR.     

Writing–erasing properties and characterizations of hybrid materials based on disperse red by sol–gel process

We investigated the synthesis and writing–erasing properties of three different hybrid materials (SGDR1, SGDR13 and SGDR19) based on disperse red by the sol–gel process. The sol–gel process was undergone using tetraethyl orthosilicate (TEOS) as a precursor. Optical properties of three hybrid materials are compared as structurally similar materials (SGDR1, SGDR13 and SGDR19). The diffraction efficiency, reversible photoinduced process and writing–erasing properties of hybrid materials were measured as a function of time. The diffraction efficiencies of SGDR1, SGDR13, and SGDR19 films were observed up to a level of 0.65%, 0.24%, and 0.99%, respectively. AFM view of the surface relief grating on the SGDR19 film showed a depth of 15 nm and a surface distance of 2.50 μm.     

Processing and characterization of sol–gel fabricated mixed metal aluminates

Nanocrystalline lanthanum aluminate (LaAlO₃, LAP) and Sr-substituted LAP ceramics were synthesized by sol–gel processes using mixtures of inorganic salts of the respective elements. The metal ions, generated by dissolving metal nitrates or acetates in acetic acid and/or water were complexed by 1,2-ethanediol to obtain the precursor for LAP. The XRD patterns of the LaAlO₃ and La_1−xSr_xAlO_3−δ (x ≤ 0.50) ceramic sintered at 1000 °C were almost identical with the perovskite LAP composition. The phase transformations, composition and microstructural features in the gels and polycrystalline samples were studied by thermal analysis (TG/DTA), powder X-ray diffraction analysis (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and inductively coupled argon plasma emission spectroscopy (ICP). The quality of the resulting products (homogeneity, crystallisation temperature, grain size and grain size distribution, etc.) of the “chimie douce” synthetic route is discussed.     

Sol–gel coatings on metals for corrosion protection

Sol–gel protective coatings have shown excellent chemical stability, oxidation control and enhanced corrosion resistance for metal substrates. Further, the sol–gel method is an environmentally friendly technique of surface protection and had showed the potential for the replacement of toxic pretreatments and coatings which have traditionally been used for increasing corrosion resistance of metals. This review covers the recent developments and applications of sol–gel protective coatings on different metal substrates, such as steel, aluminum, copper, magnesium and their alloys. The challenges for industrial productions and future research on sol–gel corrosion protective coatings are also briefly discussed.     

Silica based organic–inorganic hybrid nanocomposite coatings for corrosion protection

Silica based organic–inorganic hybrid nanocomposite coatings have been developed for corrosion protection of 1050 aluminum alloys by dip coatings technique. The hybrid sols were prepared by hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and tetramethoxy silane (TMOS) in the presence of an acidic catalyst and bisphenol A (BPA) as cross-linking agent. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. Structural characterization of the hybrid coatings were performed using optical microscopy, scanning electron microscopy (SEM) and attenuated total reflectance-infrared (ATR-IR) spectroscopy. Corrosion resistance properties of the hybrid sol–gel coatings were studied by potentiodynamic scanning (PDS) and salt spray testing methods. The results indicate excellent barrier protection performance of the coatings. In addition, the effect of molar ratio of GPTMS–BPA (silane content) on corrosion resistance of the coatings was investigated. The PDS results demonstrated that the corrosion resistance of hybrid coatings improved by decreasing of silane content.