On the Feasibility of Growing Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 Single Crystals

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by two methods: from solution using PbO as a self‐fluxing agent (SC method) and directly from the melt without fluxing (MC method). In both growth methods, an allomeric Pb[(Mg_1/3‐Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal was used as a seed. X‐ray diffraction patterns of ground crystals showed that phase‐pure perovskite PZNT91/9 single crystals were successfully fabricated by the above two methods. The composition of the crystals obtained by both the SC and MC methods was analyzed using X‐ray fluorescence, which confirmed that the crystal composition is close to the nominal value, although volatilization of PbO and segregation during crystal growth are inevitable. The MC PZNT91/9 crystals exhibit excellent piezoelectric properties, with the piezoelectric constant, d₃₃, in the range of 1800–2200 pC N^–1. This value is comparable to that of the SC crystals. However, the MC crystals show an abnormal dielectric behavior. In contrast with the SC crystals, in the MC crystals a much broader dielectric peak appears in the dielectric response curves, accompanied by a much lower peak temperature of around 105 °C. Furthermore, frequency dispersion is apparent over a much wider temperature range (even more apparent than in pure relaxors), where a large, i.e., about 70 °C, full width at half maximum (FWHM) for the dielectric peaks is observed in the dielectric response. It is speculated that such an unusual phenomenon correlates with defects, microinhomogeneities, and polar regions in the as‐grown MC crystals. The origins of this abnormality have not been interpreted in detail until now. However, optical observation of the domain structure confirms that both the SC and MC crystals possess complex structural states.     

Catalytic feasibility of Ce-doped LaCoO3 systems for chlorobenzene oxidation: An analysis of synthesis method

A family of Ce-doped LaCoO₃ perovskites are presented as possible catalysts for Cl–VOCs elimination. These materials with different contents of Ce were obtained through the citrate and the reactive grinding methods. The insertion of Ce in the original perovskite structure favours the presence of Co²⁺/Co³⁺ and Ce³⁺/Ce⁴⁺ redox pairs and a higher content of oxygen vacancies that enhances the catalytic performance in chlorobenzene combustion based on differential kinetics studies. The family obtained by the grinding method presents a performance as high as that synthesized by citrate method. Thus, the reactive grinding is a feasible green chemistry alternative to obtain a catalyst with the same performance as that obtained from traditional methods. Finally, the stability of samples was evaluated under total combustion reaction conditions showing an excellent activity during 45 h time on stream.     

Oxygen transport in ferrite-based ceramic membranes: Effects of alumina sintering aid

Moderate additions of Al₂O₃ to strontium ferrite-based mixed conductors, such as SrFe_0.7Al_0.3O_3−δ and La_0.2Sr_0.8Fe_0.8Ga_0.2O_3−δ with the composition close to the solid solution formation limits, make it possible to improve ceramics sinterability, to increase oxygen permeability and to decrease thermal expansion. These effects are associated with the segregation of alumina-rich phases, primarily SrAl₂O₄, and the formation of A-site cation-deficient perovskite. The improved properties of the SrFe_0.7Al_0.3O₃-based material were used to fabricate high-quality tubular membranes for methane conversion reactors. Similar enhancement in sinterability is also observed for another promising parent material of mixed-conducting membranes, La_0.5Sr_0.5FeO_3−δ. However, extensive dissolution of Al³⁺ cations in the iron sublattice, creation of A-site vacancies and changing the La:Sr concentration ratio all lead to decreasing ionic transport in La_0.5Sr_0.5FeO_3−δ. As a result, additions of either Al₂O₃ or SrAl₂O₄ have a deteriorating influence on the oxygen permeation fluxes through La_0.5Sr_0.5FeO₃-based ceramics.     

Aerosol deposition of dense lead zirconate titanate thin films at room temperature

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) films were grown on silicon 1 0 0 substrate by aerosol deposition, using solid-state reacted powder containing donor oxide Nb₂O₅, while the substrate was maintained at room temperature. The PZT films were simultaneously sintered upon deposition on a highly densified ceramic layer. Crystalline phases of the deposited films have been determined by X-ray diffractometry (XRD), and microstructures analysed by transmission electron microscopy (TEM). The cross-section microstructure consisted of several thin layers, including the PZT film and the platinum electrode and titanium-buffered layers on the substrate. High-resolution images revealed that the PZT layer contained a mixture of randomly oriented grains of nanometre size, which were embedded in an amorphous matrix. In contrast to the conventional liquid-phase sintering mechanism, sintering of the PZT films involved amorphised phases generated by pressure-induced amorphisation (PIA) from plastic deformation when the initial powder particles collided amongst one another upon reaching the silicon substrate during aerosol deposition. An analogy may be drawn to the impact of extraterrestrial meteorites in which diaplectic glass, i.e., amorphised phase, was formed and retained metastably at room temperature. The individual PZT grains were joined with the amorphised phase(s) and sintered to become a dense, thin film on the silicon substrate.     

Enthalpy recovery of gases issued from H2 production processes: Activity and stability of oxide and noble metal catalysts in oxidation reaction under highly severe conditions

Oxidation activity and stability under reaction was investigated for a series of mixed oxide catalysts, doped or not by a precious metal (Pd, Pt). The reaction feedstock, containing CO, H₂, CH₄, CO₂ and H₂O, simulated gases issued from H₂ production processes for fuel cells. Contrarily to conventional noble metal catalysts, mixed oxide samples present generally good stability under reaction at high temperature. The activities measured for the perovskite and hexaaluminate catalysts, are however largely lower than that of the reference Pd/Al₂O₃ catalyst. High activities were obtained after impregnation of 1.1 wt.% Pd or 0.8 wt.% Pt on the hexaaluminates samples. Even if Pd/Al₂O₃ was found to present a high activity, this sample suffered from drastic deactivation at 700 °C. Better stability were obtained on perovskite. Furthermore, doping hexaaluminate by Pt led to samples with good activities and high stability. Even if better activities were obtained by doping the hexaaluminate samples by Pd, the Pd/BaAl₁₂O₁₉ strongly deactivated, as it was previously observed for the reference catalyst. Interestingly, this Pd deactivation was not observed when Pd was impregnated on the Mn substituted hexaaluminate, leading to a stable and active catalyst. This suggests that it is possible to stabilize the palladium in its oxidized form at high temperature (700 °C) on the surface of some supports.     

Ethanol combustion over strontium- and cerium-doped LaCoO3 catalysts

Ce- or Sr-doped LaCoO₃ bulk perovskites were prepared by citric acid method as well as 10 wt.% of LaCoO₃ was deposited on alumina carrier stabilized with lanthanum. Properties of prepared materials were characterized by determination of surface area, acid-basic properties and XRD, XPS, TPDO₂, H₂-TPR measurements as well as catalytic activity and selectivity for ethanol combustion was tested. It was found that substitution of La in LaCoO₃ with either Sr or Ce has only small effect on its activity in ethanol combustion. Strontium inserted into LaCoO₃ structure increases basic character of the perovskite surface as well as selectivity to acetaldehyde (ACA). Substitution of La with cerium has no effect on the concentration of basic sites and does not affect the selectivity to ACA. Activity of LaCoO₃-based catalysts in ethanol combustion and their selectivity to ACA formation can be explained on the basis of the presence of both -oxygen species and sites with basic character on the material surface.

Acid-basic properties of supported LaCoO₃ are dominated by acidic character of the carrier. Results of XPS and H₂-TPR measurements of LaCoO₃ supported on La–Al₂O₃ suggest that perovskite remains in strong interaction with carrier and probably is partially decomposed. Deposition of perovskite on stabilized carrier significantly increases the rate of ethanol combustion.     

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.     

Sintering behaviour of La1−xSrxFeO3−δ mixed conductors

The sintering properties of La_1−xSr_xFeO_3−δ (x = 0.1, 0.25) mixed conductors have been investigated with particular emphasis on the effect of secondary phases due to cation non-stoichiometry (±5 mol% La excess and deficiency). Secondary phases, located at grain boundaries in cation non-stoichiometric materials, increased the sintering temperature compared to single-phase materials. Extensive swelling in final stage of sintering was observed in all materials, which resulted in micro-porous materials. The swelling was most pronounced in the phase pure and two-phase materials due to La-deficiency, while refractory secondary phases in La-excess materials inhibited both sintering, grain growth and swelling. In La-deficient materials, formation of molten secondary phases resulted in rapid swelling due to viscous flow. The present findings demonstrated the importance of controlling sintering temperature and time, as well as careful control of the cation stoichiometry of La_1−xSr_xFeO_3−δ in order to achieve fully dense and homogenous La_1−xSr_xFeO_3−δ ceramics.