Rheological behaviour and spectroscopic investigations of cerium-modified AlO(OH)colloidal suspensions

The rheological behaviour of aqueous suspensions of boehmite (AlO(OH)) modified with different Ce-salts (Ce(NO3)3, CeCl3, Ce(CH3COO)3 and Ce2(SO4)3) was investigated at a fixed Ce/Al molar ratio (0.05). Freshly prepared boehmite suspensions were near-Newtonian and time-independent. A shear-sensitive thixotropic network developed when Ce-salts with monovalent anions were introduced in the nanoparticle sols. The extent of particle aggregation dramatically increased with ageing for Ce(NO3)3 and CeCl3 whereas an equilibrium value was reached with Ce(CH3COO)3. The addition of Ce2(SO4)3 with divalent anions involved no thixotropy but rather a sudden phase separation. The combined data set of IRTF and DRIFT spectra indicated that free View the MathML source anions of peptized boehmite adsorb on the nanoparticle surface by H-bond. The introduction of Ce-salts in the boehmite sol led to the coordination between Ce3+ ions and View the MathML source anions adsorbed on boehmite i.e. to [Ce(NO3)4(H2O)x]− complex. Such coordination led to a thixotropic behaviour which was lower with Ce(NO3)3 compared to CeCl3 and Ce(CH3COO)3. In contrast, Ce2(SO4)3 formed insoluble complexes with dissolved aluminium species. The formation of H-bonded surface nitrate complexes was found to play a decisive role on the particle–particle interactions and consequently on the rheological behaviour of the sols

An efficient route to aqueous phase synthesis of nanocrystalline γ-Al2O3 with high porosity: From stable boehmite colloids to large pore mesoporous alumina

In this paper we emphasise the important role of Pluronic F127 on the porosity of mesoporous alumina prepared from boehmite colloids. By focusing on the F127/boehmite interactions we show how the concepts of interface science may help to predict and improve the textural characteristics of mesoporous alumina. By varying the synthetic parameters, in particular the copolymer content, we show that the porosity of c-Al2O3 can be enhanced by 400% and the average pore diameter can be expanded from 5 to 14 nm. These results are discussed in terms of interactions between the Pluronic F127 and boehmite colloids, and are correlated to the critical micelle concentration (CMC) of the copolymer. The textural characteristics of the mesoporous alumina can be further improved either by introducing hydrocarbons in the preformed boehmite/copolymer sols or by concentrating the sols. In comparison with as-synthesised alumina, those prepared with F127 showed improved thermal stability. Furthermore, boehmite/copolymer sols were stable for all surfactant concentrations investigated and can give high quality coatings suitable for catalytic applications

Electrophoretic silica-coating process on a nano-structured copper electrode

A method for silica-coating at the nanoscale by electrophoretic deposition is presented here, using raw or grafted silica dispersions

Improvement of barrier properties of a hybrid sol-gel coating by incorporation of synthetic talc-like phyllosilicates for corrosion protection of a carbon steel

Sol–gel coatings for corrosion protection of metals are a good alternative to toxic chromate treatments. The present work focussed on the incorporation of inorganic fillers in a sol–gel coating to improve the barrier properties of the film. Talc-like phyllosilicates obtained by hydrothermal synthesis at 160°C, 260°C and 350°C, called T160, T260 and T350 respectively, were selected as inorganic fillers. The synthetic materials showed talc lamellar structure but, in contrast with natural talc, their smaller size (about 300 nm) and their hydrophilic character allowed easier dispersion of the particles in the sol–gel matrix. Electrochemical impedance measurements performed on the sol–gel coatings deposited on XC35 carbon steel showed that the incorporation of T260 and T350 at a concentration of 20 g L− 1 strongly enhanced the barrier properties of the coating by comparison with the filler-free system. As a consequence, the corrosion protection of the metal substrate was improved

Bulk or surface grafted silylated Ru(ii) complexes on silica as luminescent nanomaterials

A series of Ru(II) complexes with monosilylated-dipyridine ligand have been synthesized and fully characterized and were then covalently attached to silica nanoparticles. Two types of hybrids were obtained depending on the experimental procedure. In the first approach, metal complexes were incorporated inside the silica nanoparticles leaving a free hydroxylated silica surface for further functionalization. These silica based nanohybrids are similar to the well known nanoparticles encapsulating [Ru(bpy)3]2+ complexes preventing the release of the dye when used in aqueous or organic solutions. Size and luminescence properties vary throughout the series of metal complexes. The second approach leads to ruthenium(II) complexes covalently attached to the silica nanoparticle surface via hydrolysis and condensation of the ethoxysilyl group with silanol sites of Ludox type silica nanoparticles. This leads to the grafting of a monolayer for complexes with the monoethoxysilyl dipyridine ligand. In contrast, the complexes with triethoxysilyl ligands can lead to small amounts of oligomers, but their quantity is limited by the sterical constraints imposed by the molecular structure. The size of the hybrids depends on the starting particles. 29Si and 13C solid state NMR are used to characterize silica surface properties whereas TEM and SEM confirm nanosize and morphology of the hybrids. The complexes and the nanohybrids are luminescent, with variations for ruthenium(II) complexes that are covalently incorporated or grafted on the silica surfac

Functionalization of synthetic talc-like phyllosilicates by alkoxyorganosilane grafting

A range of talc-like phyllosilicates were prepared via a hydrothermal synthesis performed at five different temperatures from 160 to 350 °C. The organization of the lattice and the degree of crystallinity of the new materials were evaluated by different techniques such as XRD, FTIR, solid-state 29Si NMR, TEM, FEG-SEM and TG-DTA. When synthesized at low temperature the material presents high degree of hydration, low crystallinity and flawed structure. This was attributed to stevensite-talc interstratified product present in the samples. The stevensite/talc ratio and the hydration decrease in the talc-like phyllosilicate samples when the hydrothermal synthesis temperature increases and so the crystallinity becomes higher. A thermal treatment at 500 °C allowed a significant flaw reduction in talc-like phyllosilicate structure; the synthesized sample at 350 °C and heat treated presents a structure close to that of talc. The different talc-like phyllosilicates were grafted covalently by two organoalkoxysilane reagents, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (IM2H) and 2-hydroxy-4-(3-triethoxysilylpropoxy)-diphenylketone (HTDK). The grafted amounts of the hybrids, determined by elemental analysis and confirmed by thermogravimetric data, are dependent on the hydrothermal synthesis temperature and organoalkoxysilanes; they become smaller when the synthesis temperature increases and when HTDK is used. FTIR and solid-state 13C CP MAS NMR were applied to characterize the grafted organic groups. So, in this work it is shown that by choosing the hydrothermal synthesis temperature or by performing an additional annealing it is possible to adjust the amount of defects in the structure of talc-like phyllosilicates which seems to be strongly correlated to the grafting performance

Protection against corrosion of magnesium alloys with both conversion layer and sol–gel coating

The anticorrosion performances of a system consisting of a phosphate based conversion layer and a hybrid sol–gel coating have been evaluated for the magnesium alloy Elektron21. The lone sol–gel coating affords a significant protection of the magnesium substrate. However, the presence of an intermediate conversion layer is presumed to improve the corrosion resistance of the system. The surface morphology of the protection coatings was characterized by optical microscopy, scanning electron microscopy (SEM) and white-light source interferometry. The corrosion behavior of the systems was analyzed by electrochemical impedance spectroscopy (EIS). The impedance measurements show that the presence of the added conversion layer increases the resistance of the whole system during immersion in a 0.05 M NaCl solution, compared to the single sol–gel coating

New green coatings made from fatty acid dispersions: improvement in barrier properties of biodegradable thermoplasticized-starch substrate

This work was aimed at developing new coatings on biodegradable substrates for possible use in food packaging. In order to study barrier properties of these coatings made from fatty acid dispersions, oxygen permeability, water vapor permeability and also contact angle measurements were carried out. The coatings made from a fatty acid exhibited good barrier properties towards oxygen gas. Moreover, these coatings presented a higher contact angle value than the one obtained directly for the substrate without coating; this can be likely due to the hydrophobic nature of fatty acid and the recrystallization of fatty acid during the drying process

Ce(III) corrosion inhibitor release from silica and boehmite nanocontainers

Electrochemical impedance spectroscopy clearly appeared as a suitable technique to investigate the releasing properties of cerium (III) loaded on silica and boehmite nanocontainers. In this way the electrochemical behavior of the AA2024-T3 was evaluated by electrochemical impedance spectroscopy in a 0.045 mol L−1 NaCl solution with nanocontainers containing the inhibitor. Results show that the inhibitor release is influenced by both the chemical nature and the morphology of the nanocontainers. The lower loading and release phenomena were observed for the mesoporous silica nanocontainers, whereas the inhibitor is liberated until 168 h from dense silica nanocontainers. Boehmite nanocontainers combine a good loading ratio with a longer release until the second week of immersion

An Artificial Interface for High Cell Voltage Aqueous-Based Electrochemical Capacitors

Aqueous electrolytes are very effective for supercapacitor applications but their narrow electrochemical potential window (∼1 V) and associated limited energy currently limits their use. Here, we demonstrate a new strategy to enlarge the potential window by designing an artificial interface (ai). An effective ai was achieved via a mixture of siloxanes doped with an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI). Indeed, the as-deposited ai on the carbon-based electrode hinders the electron charge transfer but not the ionic charge transfer, making the ai ionic conductive. As a result, a cell voltage of about 1.8 V was obtained in aqueous electrolyte-EMI HSO4 1 mol l−1 in water. Used as a membrane, the ai was found to be ionically specific to EMI+; the proton transference number being close to zero. These results show the strategy of developing an ai at the electrode/electrolyte interface could represent a new path for aqueous-based carbon-carbon supercapacitors to reach higher cell voltages, providing both higher specific energy and power