Mechanosynthesis of complex oxides and preparation of mixed conducting nanocomposites for catalytic membrane reactors

Nanopowders of LaGaO₃- and LaMnO₃-based complex perovskites (P) and ceria-based fluorites (F) were prepared by mechanosynthesis. Compatible nanocomposites F + P and P + P with mixed ion and electron conducting (MIEC) properties were prepared and sintered at moderate temperatures up to dense ceramics. The obtained materials were studied by means of XRD, SEM, TEM, electrical conductivity measurements, temperature programmed (TP) reduction/oxidation and preliminary estimations of permeability were obtained. A new strategy based on the advantages of the mechanochemical ceramic approach is proposed to design multilayer ceramic membranes for CMR. Casting technology and one-step sintering were used for the production of thin film membranes with MIEC properties on porous substrates. The coarse fraction of as-milled powders from agglomerates with density 70% was used for the porous substrate, and fine fractions of aggregates with sizes <1 μm were used in preparation of composites for thin dense films. Ceria-based composites prepared by the Pechini route and/or mechanochemical method are proposed as materials for protecting thin films.     

Analysis of the rhombohedral–tetragonal symmetries coexistence in lead-free 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics from nanopowders

Ceramics with perovskite-type structure and 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (BNBT) composition have been studied by conventional powder X-ray diffraction in Bragg–Brentano geometry. Ceramics were obtained from sol–gel autocombustion nanopowders and processed either by hot pressing and subsequent recrystallisation or pressureless sintering in two steps. These methods provided single-phase, sub-micron grain size (<700?nm), dense ceramics with good piezoelectric performance (96–94% of theoretical density and d₃₃?=?143–124?pC?N^–1, respectively). For the considered ceramics, the splitting of the peaks of the cubic perovskite-type structure with 111 and 200 Miller indices has been repeatedly used as a symmetry identification criterion. In this work a simple, yet powerful, procedure to validate the consistency of the mentioned splitting interpretation is presented. Based on peaks fitting and well-known crystallographic expressions, the rhombohedral and tetragonal symmetries' coexistence is verified. The suggested procedure can be applied to the study of peak splitting in ceramics at Morphotropic Phase Boundaries in a general way. In a given series of BNBT ceramics, inconsistencies for interplanar distances, intensities' ratios and the evolution of these from not-poled to poled samples have been found. In poled ceramics, special care has been taken when carrying out this analysis, due to the anisotropic strains arising from ferroelectric (FE) domain orientation. Poling gives rise to a displacement of the peaks angular positions and modification of the intensity ratios. However, the interplanar distance changes associated with the angular deviations here observed are one order of magnitude higher than those expected from anisotropic strains. These results set up a doubt on the sufficiency of the [rhombohedral?+?tetragonal] model to characterise the considered ceramics. A model of a mesoscopic FE phase with rhombohedral symmetry, a mesoscopic and globally weakly polar phase, with cubic symmetry, and a nanosised phase, also cubic, is presented as a plausible alternative.     

Synthesis,densification and characterization of Ag doped ceria nanopowders

Nanosized Ag-doped ceria (Ce_1-xAl_xO_2-δ)powders (0.1 ≤ x ≤ 0.04) were obtained by self-propagating room temperature reaction. The solid solubility of Ag into ceria lattice was the highest reported so far. X-ray diffraction analysis and field emission scanning microscopy results showed that the doped samples are single phase solid solutions with fluorite-type structure and all prepared powders were nanometric in size. The average size of Ce1-xAgxO2-▯ particles lies at about 4 nm. Raman spectra revealed an increase in the amount of oxygen vacancies with the increase of Ag concentration, such as is foreseen. The thermal stability of solid solution was followed by XRD. Microstructure development was studied by scanning electron microscopy. By controlling the processing variables, it was possible to obtain high density samples with homogeneous microstructure at low sintering temperature.     

Densification of rare-earth (Lu, Gd, Nd)-doped alumina nanopowders obtained by a sol-gel route under seeding

Rare-earth (RE: Lu, Gd, Nd, 0.10 mol%)-doped alumina nanopowders were prepared by a new sol-gel route using polyhydroxoaluminum (PHA) and RECl₃ solutions under α-alumina (∼ 75 nm) seeding. Among the rare-earth dopants studied, Lu yields the most suitable nanopowders for low-temperature densification. The 0.10 mol% Lu-doped nanopowders, which were obtained at a calcination temperature of 900 °C under 5 mass% α-alumina seeding, consisted of ∼ 80-nm α-alumina particles and γ-alumina nanoparticles. Using these Lu-doped alumina nanopowders, fully densified alumina ceramics with a uniform microstructure composed of fine grains with an average size of 0.61 μm could be obtained at 1400 °C by pressureless sintering. Clearly, the Lu-doped nanopowders obtained here represent a viable option for fabricating dense, finer-grained alumina ceramics because an undoped sample with 5 mass% seeds gave a microstructure with an average grain size of 1.78 μm at 1400 °C.     

Hydrothermally Processed Oxide Nanostructures and Their Lithium–ion Storage Properties

Y- and Si-based oxide nanopowders were synthesized by a hydrothermal reaction of Y or Si powders with NaOH or LiOH aqueous solution. Nanoparticles with different morphology such as elongated nanospheres, flower-like nanoparticles and nanowires were produced by a control of processing parameters, in particular, the starting composition of solution. The preliminary result of electrochemical examination showed that the hydrothermally processed nanowires exhibit high initial capacities of Li-ion storage: 653 mAh/g for Y₂O₃ nanowires as anode materials and 186 mAh/g for Li₂Si₂O₅ nanowires as cathode materials in a Li secondary cell. Compared to the powder with elongated sphere or flower-like shapes, the nanowires showed a higher Li-ion capacity and a better cycle property.     

Effect of vibro-milling time on phase formation and particle size of lead zirconate nanopowders

A perovskite phase of lead zirconate, PbZrO₃, nanopowder was synthesized by a solid-state reaction via a rapid vibro-milling technique. The effect of milling time on the phase formation and particle size of PbZrO₃ powder was investigated. Powder samples were characterized using TG-DTA, XRD, SEM and laser diffraction techniques. It was found that an average particle size of 50 nm was achieved at 25 h of vibro-milling after which a higher degree of particle agglomeration was observed upon continuation of milling to 35 h. In addition, by employing an appropriate choice of milling time, a narrow particle size distribution curve was also observed.     

Plasmon-enhanced luminescence of YAG: Yb, Er nanopowders by Ag nanoparticles embedded in silicate glass

Solid-state field-assisted diffusion was used to prepare Ag nano-composite silicate glass. After positive diffusion process, small Ag atoms clusters were formed in the slides. The Ag atom clusters could aggregate into Ag nanoparticles (NPs) with bigger size after subsequent reverse diffusion process. YAG: Yb, Er nanopowders were screen-printed on the glass slides after positive and reverse diffusion, respectively, for up-conversion luminescence measurement. Almost no luminescence enhancement was observed for the slide after positive diffusion. Whereas, obvious enhancement was obtained for the slide after reverse diffusion, and the enhancement factor could reach about 26. The strong enhancement was due to the larger size of Ag NPs. The present work suggested a new promising method to enhance the luminescence of YAG: Yb, Er nanopowders.     

Preparation of tantalum nanopowders through hydrogen reduction of TaCl5 vapor

Tantalum powders, ranging from 14 to 56 nm in primary particle size, were produced through hydrogen reduction of TaCl₅ vapor in a furnace aerosol reactor. The mass of the precursor, solid TaCl₅, was instantaneously measured during vaporization with a load cell to determine and control the precursor concentration at the reactor inlet. Tantalum pentachloride to tantalum conversion was 35% and 98% at 1000 and 1400 °C, respectively. The primary particle size increased with increasing the evaporator temperature and the hydrogen flow rate. The tantalum powder produced was amorphous at 1000 °C and crystalline at 1400 °C. The XRD peaks of the as-produced powders shifted towards lower angles due to the partial dissolution of hydrogen in the tantalum. Upon removal of the hydrogen through heat treatment in a vacuum, the shift disappeared. The oxygen content of the powder was 6.0 to 6.9 wt.%, with an oxide layer about 3 nm thick formed on individual particles. Through thermogravimetric analysis in air, the powders were found to be resistant to further oxidation at up to 200 °C, but to have been completely oxidized at 400 °C.     

Breakage of TiO2 agglomerates in electrostatically stabilized aqueous dispersions

Nanoparticles of metal oxides have applications as additives in thin nanocomposite films. For optical applications that include transparent films and coatings, nanoparticles should be uniformly dispersed in the polymer film. Most commercially available nanoparticles are large agglomerates about 1 μm in maximum dimensions composed of primary particles with sizes ranging from 5 to 50 nm. The large agglomerates scatter light and are not directly suitable for optical systems. Ultrasonication of liquid suspensions was used to prepare stable dispersions from commercial titania nanopowders. The mean diameter of sonicated titania nanopowders was correlated inversely to the specific energy. After a rapid initial size reduction, continued ultrasonication lead to insignificant reduction and even reagglomeration of the particles. Both erosion and fracture mechanisms were observed. None of the commercial nanopowders were successfully broken to their primary particle sizes. Reagglomeration of the dispersion could be prevented by electrostatic stabilization with nitric acid or ammonium hydroxide when its zeta potential value was less than − 30 mV or greater than + 30 mV.     

Influence of synthesis conditions on the properties of Y2O3–MgO nanopowders and sintered nanocomposites

In this study, a citrate–nitrate combustion method was applied to synthesize composite Y₂O₃–MgO nanopowders. In order to optimize the synthesis condition to support sufficient combustion, the molar ratio of citric acid to nitrate (c/n molar ratio) used in the reaction mixtures was varied between 0.17 and 0.34. Nanopowders with an average particle size of 17 nm were achieved. The properties of these nanopowders indicated that the higher molar ratios decreased the unreacted organic components and increased the amount of carbide on the surface of the oxides, which helped to inhibit the formation of carbonate groups. The amount of carbonate groups was reduced with the increasing c/n molar ratio. Y₂O₃–MgO nanocomposites fabricated through hot-isostatic-pressing sintering showed a uniform distribution of Y₂O₃ and MgO grains, which had an average size of ∼180 nm. In addition, the absorption peaks at 1410 and 1511 cm⁻¹ disappeared until the c/n molar ratio reached 0.28. A high average infrared transmittance of 83% in the range of 4000–1667 cm⁻¹ (2.5–6 μm) was obtained in the nanocomposites.