Low temperature synthesis of aluminium titanate by an aqueous sol-gel route

Formation of aluminium titanate (AT) has been achieved at low temperature through sol-gel process using boehmite and titanium hydroxide as precursors by controlling the particle size at nanoscale followed by in-situ peptisation. The formations of AT phase, particle size distributions, sintering and thermal expansion characteristics, and microstructural features have been reported. DTA and XRD analysis have been performed to confirm the formation of AT. A 94% relative density was obtained for aluminium titanate sintered at 1550 °C with controlled grain size in the range of 2-3 μm.     

Synthesis by sol-gel route and characterization of Yttria Stabilized Zirconia coatings for thermal barrier applications

This paper deals with the development of new synthesis techniques for functional materials such as Yttria Stabilized Zirconia (YSZ) used in the field of thermal barriers coatings. Currently, Thermal Barrier Coatings (TBCs) are manufactured by dry route technologies (EB-PVD or plasma spray) but such methods are directional and often require costly investments and complicated operations. We have carried out significant work aimed at developing sol-gel routes, which are nondirectional methods, to prepare, by suitable chemical modifications, nanocrystalline materials with a controlled morphology. The main advantage of this method is to decrease the crystallization temperature, much lower than the conventional processes, allowing the synthesis of reactive powders with nanometric particles size. In this paper, the formulation of an alkoxide sol has been optimized in order to obtain homogeneous YSZ films. Nature and quantity of binders have been studied. Superalloys have been then immersed in the sol and withdrawn at several controlled rates before being annealed at different temperatures. The films microstructures have been investigated using scanning electron microscopy. It appears that the combination of a slower withdrawal speed (17 cm/min) with a 3 wt.% content of DBP allows to obtain the most homogeneous and the thicker coatings. Moreover, SEM-FEG observations have shown that the deposit is present all over the rough surface of the substrate and is composed of two morphologies: a YSZ thin covering film and a thicker discontinuous layer duplicating the substrate topography.     

Preparation of submicrometer-sized titania hollow spheres by templating sulfonated polystyrene latex particles

Submicrometer-sized titania hollow spheres with tunable shell thickness and smooth surfaces have been successfully synthesized by employing sulfonated polystyrene (PS) latex particles as a template in sol-gel method. The structure of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The shell thickness was readily tuned by altering the concentration of titanium tetrabutoxide (TBOT) in ethanol solutions. The surface roughness as well as the shell thickness has the tendency to increase with the increase in the concentration of TBOT. The diameter of the hollow spheres was on the average of 20-26% smaller than the diameter of template PS latex particles. Some titania fragments were also observed for the sample with the highest TBOT concentration.     

Sol-gel Preparation and Preliminary in vitro Evaluation of Fluorapatite／Hydroxyapatite Solid Solution Films

Fluorapatite/hydroxyapatite solid solution has better biological properties than other apatites, especially used as films or coatings. In this work, sol-gel preparation and in vitro behavior of fluorapatite/hydroxyapatite solid solution films on titanium alloy were investigated. Ca(NO3)2-4H20 and PO(OH)x(OEt)3-x were selected as precursors, and hexafluorophosphoric acid (HPFo) was used as a fluorine containing reagent. The Ca and P precursors were mixed with HPFo to keep the Ca/P molar ratio 1.67. The mixtures refluxed for 12 h were used as dipping sols for the preparation of the films. The phase of the films obtained at 600℃ was apatite. The F contents in the films increased with the concentrations of HPF6 in the dipping sols. The solid solution films were shown to have better stability than hydroxyapatite films, and a reasonably good bioactivity in the in vitro evaluation.     

Sol-gel processing: A versatile concept for special glasses and ceramics

The various parameters related to sol-gel processing are discussed with special reference to those which usually attract less attention but depending on the final product in mind, can play important roles. The versatility of the sol-gel technique in materials preparation is demonstrated by discussing the various products developed at the author’s laboratory by using this processing method.     

Sol-gel preparation of a di-ureasil electrolyte doped with lithium perchlorate

Solid polymer electrolytes (SPEs) synthesized by the sol-gel process and designated as di-ureasils have been prepared through the incorporation of lithium perchlorate, LiClO₄, into the d-U(2000) organic-inorganic hybrid network. Electrolytes with lithium salt compositions of n (where n indicates the number of oxyethylene units per Li⁺ ion) between ∞ and 0.5 were characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode, thermal analysis and Fourier transform Raman (FT-Raman) spectroscopy. The conductivity results obtained suggest that this system offers a quite significant improvement over previously characterized analogues doped with lithium triflate [S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Barros, M.J. Smith, R.A. Sá Ferreira, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. Soc. 152 (2) (2005), A429]. “Free” perchlorate ions, detected in all the samples examined, are identified as the main charge carriers in the sample that yields the highest room temperature conductivity (n = 20). In the di-ureasils with n ≤ 10 ionic association is favoured and the ionic conductivity drops.     

Zirconium tetra-n-butylate modified with different organic acids: Hydrolysis and polymerization of the products

In this work, (a) complexation reaction of zirconium tetra-n-butylate, Zr(OBu ⁿ )₄, with MAc and different organic acids, (b) the hydrolysis reaction of modified Zr species, and (c) the polymerization reaction of complex products are studied. Zr(OBu ⁿ )₄ was reacted with different mole ratios of methacrylic acid (MAc) at room temperature and the maximum combination ratio was found to be 1:2 [Zr(OBu ⁿ )₄:MAc] by FT-IR. The modification of zirconium tetra-n-butylate with the acid mixtures [methacrylic acid-acetic acid (MeCOOH), methacrylic acid-propionic acid (EtCOOH), methacrylic acid-butyric acid (PrCOOH)] was made for a combination ratio of 1:1:1 [MAc:RCOOH:Zr(OBu ⁿ )₄; R: Me, Et, Pr] and the products were characterized by¹H-NMR, FT-IR, and UV spectroscopies. Following their synthesis, hydrolysis of the complexes with various amounts of water and polymerization with benzoyl peroxide were realized. The hydrolysis and polymerization products of the complexes were studied by Karl-Fischer coulometric titration and thermal analysis, respectively. Methyl ethyl ketone(MEK) and chloroform were chosen as solvents.     

The properties of electroactive ruthenium oxide coatings supported by titanium-based ternary carbides

Electroactive oxide coatings on titanium, known in industrial chlorine production as dimensionally stable anodes (DSA), are of limited service life owing to the dissolution of active oxide, but also due to low corrosion stability of titanium, at high anodic potentials and elevated temperatures. In order to improve the anode stability, ternary carbide, Ti₃SiC₂, could be a promising material for the coating support, since chemical corrosion stability of Ti₃SiC₂ is significantly higher if compared to Ti. In this work, the possibility of the sol-gel preparation of RuO₂-TiO₂ coating on Ti₃SiC₂ is investigated and comparison of the basic characteristics of sol-gel processed oxide coating, Ru_0.5Ti_0.5O₂, applied onto Ti₃SiC₂ and Ti, is reported. Microscopic investigation of the coating surface showed that considerably less cracked coating is formed onto the Ti₃SiC₂ support. Slightly higher voltammetric currents are registered for Ti₃SiC₂-supported coating in H₂SO₄ and NaCl solution. The activity for chlorine evolution is higher, while the currents of oxygen evolution reaction are lower for Ru_0.5Ti_0.5O₂/Ti₃SiC₂ anode in comparison to Ru_0.5Ti_0.5O₂/Ti anode. Even though these preliminary results on the basic electrochemical properties of Ru_0.5Ti_0.5O₂/Ti₃SiC₂ anode and chemical stability of Ti₃SiC₂ are promising, the accelerated stability test in NaCl solution showed that coated Ti₃SiC₂ is not anodically stable and lasts considerably shorter than Ru_0.5Ti_0.5O₂/Ti anode prepared and tested under the same conditions.