Structural and Electrical Properties of Sol–Gel-processed CdTiO3 Powders and Films

Cadmium titanate, CdTiO₃, was prepared by the sol–gel technique in bulk and in thin film form. The thermal evolution of the gels and the phase changes were studied by thermo- gravimetric analysis (TGA), X-ray diffractometry (XRD) and Raman and energy-dispersive (EDS) spectroscopies. The morphology of the samples was observed using scanning electron microscopy (SEM). Gels heated to 800 °C gave rise to powders with only the ilmenite-like phase. The orthorhombic perovskite phase is the only crystalline phase observed after a 4 h heat-treatment at 1100 °C. With respect to the conventional preparation method by solid-state reaction, by the sol–gel method it is possible to prepare the ilmenite phase at lower temperatures and the perovskite phase in a shorter time. Clear, homogeneous thin films were obtained by the dip-coating method. The refraction index and the thickness of the films were measured using ellipsometry. The humidity-sensitive electrical properties were measured for thin films deposited on alumina substrates with comb-type gold electrodes, heated to 200 °C and 450 °C. The films heated to 200 °C, which still contained organics, showed a variation of the resistance of six orders of magnitude in the relative humidity (RH) range tested (4–87% RH). The films heated to 450 °C, made of ilmenite-type CdTiO₃, were nearly insensitive to RH. © 1997 by John Wiley & Sons, Ltd.     

The thermal behaviour of the hydroxide mixtures used for the synthesis of MgFe2O4 spinel

The thermal behaviour of hydroxide mixtures, precursors to the synthesis of MgFe₂O₄ spinel powders, was investigated.The mixtures of hydroxides were prepared by coprecipitation reaction from nitrate solutions with an Mg/Fe atomic ratio of 12. The results were related to the thermal behaviour of separately precipitated components of the hydroxide mixtures. Samples prepared by mechanically mixing the separately precipitated hydroxides were also studied.The spinel formation temperature was identified by performing XRD analysis on powder samples heated to different temperatures. The presence of spinel from the thermal decomposition of coprecipitated mixtures was detected at a temperature as low as 380°C. The separate formation of MgO and Fe₂O₃ from the thermal decomposition of mechanical mixtures was observed; nevertheless the formation of MgFe₂O₄ through a solid state reaction between the oxides was noted at a temperature as low as 500°C.The Authors wish to thank Dr. L. Petrilli and Mr. F. Dianetti for carrying out the elemental chemical analyses at the Microanalysis Service of the C. N. R. laboratories of the Area della Ricerca di Roma.     

Low Temperature Sol-Gel Preparation of β-Al2TiO5 Thin Films: Spectroscopic Analysis of the Precursors

Two sol-gel syntheses allowed the preparation of -Al₂TiO₅ thin films on silicon substrates at 700°C, reacting aluminum and titanium alkoxides with and without acetylacetone as a chelating agent. Nuclear magnetic resonance (NMR) and mass spectra of the sols allowed identification of the intermediate species formed and to show the formation of an Al-Ti containing polymer establishing that the synthesis without acetylacetone leads to the most extensive polymerization. The formation of -Al₂TiO₅ at low temperatures is attributed to diffusion-limited crystallization process, which takes place in the conditions of high homogeneity at molecular level reached in the sol-gel synthesis. The crystallization of the films was studied as a function of the firing time and temperature and confirmed that -Al₂TiO₅ with better thermal stability was obtained with the synthesis without chelating agent.     

Sol-Gel Processed TiO2-Based Nano-Sized Powders for Use in Thick-Film Gas Sensors for Atmospheric Pollutant Monitoring

Sol-gel routes were used to prepare pure and 5 at% and 10 at% Ta- or Nb-dope TiO₂ nano-sized powders. The thermal decomposition behaviour of the precursors was studied using simultaneous thermogravimetric and differential thermal analysis (TG/DTA). X-ray diffraction (XRD) analysis showed that the powders heated to 400°C were crystalline in the anatase TiO₂ structure. The pure TiO₂ powder heated to 850°C showed the rutile structure. The addition of Ta and Nb inhibited the anatase-to-rutile phase transformation up to 950–1050°C. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired for 1 h at different temperatures in the 650–1050°C range. Scanning electron microscopy (SEM) observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at a nanometric level even at 950°C, though grain growth was observed with increasing temperature. The gas-sensitive electrical response of the thick films were tested in laboratory, in environments with CO in dry and wet air. Conductance measurements showed a good gas response only for the nanostructured titania-based films. For field tests, the prototype sensors were placed beside a conventional station for atmospheric pollutant monitoring. The electrical response of the thick films was compared with the results of the analytical instruments. The same trend was observed for both systems, demonstrating the use of gas sensors for this aim.     

Lowering grain boundary resistance of BaZr(0.8)Y(0.2)O(3-δ) with LiNO3 sintering-aid improves proton conductivity for fuel cell operation

A novel sintering additive based on LiNO(3) was used to overcome the drawbacks of poor sinterability and low grain boundary conductivity in BaZr(0.8)Y(0.2)O(3-δ) (BZY20) protonic conductors. The Li-additive totally evaporated during the sintering process at 1600 °C for 6 h, which led to highly dense BZY20 pellets (96.5% of the theoretical value). The proton conductivity values of BZY20 with Li sintering-aid were significantly larger than the values reported for BZY sintered with other metal oxides, due to the fast proton transport in the "clean" grain boundaries and grain interior. The total conductivity of BZY20-Li in wet Ar was 4.45 × 10(-3) S cm(-1) at 600 °C. Based on the improved sinterability, anode-supported fuel cells with 25 μm-thick BZY20-Li electrolyte membranes were fabricated by a co-firing technique. The peak power density obtained at 700 °C for a BZY-Ni/BZY20-Li/La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ) (LSCF)-BZY cell was 53 mW cm(-2), which is significantly larger than the values reported for fuel cells using electrolytes made of BZY sintered with the addition of ZnO and CuO, confirming the advantage of using Li as a sintering aid.     

High-performance bilayered electrolyte intermediate temperature solid oxide fuel cells

The ESB/GDC bilayer electrolyte concept has been proved to improve open circuit voltage and reduce the effective area specific resistance of SOFCs utilizing a conventional single-layer GDC electrolyte. However, high performance from such bilayer cells had not yet been demonstrated. The main obstacles toward this end have been fabrication of anode-supported thin-film electrolytes and the reactivity of ESB with conventional cathodes. Recently, an ESB-compatible low area specific resistance cathode was developed: microstructurally optimized Bi₂Ru₂O₇-ESB composites. In addition, we recently developed a novel anode functional layer which can significantly enhance the performance of SOFC utilizing GDC electrolytes. This study combines these recent achievements in SOFC studies and shows that exceptionally high performance of SOFC is possible using ESB/GDC bilayer electrolytes and Bi₂Ru₂O₇-ESB composite cathodes. The result confirms that the bilayer electrolyte and the Bi₂Ru₂O₇-ESB cathode can increase the open circuit potential and reduce the total area specific resistance. The maximum power density of the bilayered SOFC was improved to 1.95 W cm^?2 with 0.079 Ω cm² total cell area specific resistance at 650 °C. This is the highest power yet achieved in the IT range and we believe redefines the expectation level for maximum power under IT-SOFC operating conditions.     

Some structural considerations on the perovskite‐type A1‐ySryCo1‐xFexO3‐δ solid solution series

Solid solution series of La_1‐ySr_yCo_1‐xFe_xO_3‐δ were extensively studied in the past as cathode materials for solid oxide fuel cells. However, the crystal structure behavior of La_1‐ySr_yCo_1‐xFe_xO_3‐δ solid solution series when La‐ions are replaced with another rare‐earth ion or metallic alkaline earth metal is at present not fully understood. Here we report X‐ray powder diffraction measurements performed on samples of the Sm_0.8Sr_0.2Co_1‐xFe_xO_3‐δ solid solution series. This study demonstrates that the average A‐cation radius, as well as the Fe content (x), affects the structural modification of the A_1‐ySr_yCo_1‐xFe_xO_3+δ solid solution series significantly. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)