PAULO SERGIO MARTINS DA SILVA
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Resumo IPEN-doc 26122 Ceria-based ceramic composites for high temperature thermochemical applications2018 - SILVA, PAULO M.; ESPOSITO, VINCENZO; MARANI, DEBORA; FLORIO, DANIEL Z. de; FONSECA, FABIO C.Among thermochemical conversion processes, the production of fuels such as H2 via solar thermochemical cycles is potentially more efficient and more economical than the use of electric energy to electrolyze water. The principle of solar thermochemical cycles is based on the remarkable properties of some oxides, which can be reduced and oxidized cyclically (redox cycles), i.e., releasing and absorbing oxygen under certain temperature (or pressure) regimes. These redox cycles can be efficiently used to convert H2O (or CO2) to H2 (CO). Thermochemical redox cycles avoid the problematic step of fuel / O2 separation and allow operation at more moderate temperatures (~ 1500 K) [1]. In this work, a new material concept for the separation of high temperature H2O based on porous ceramic composites composed of an ultra-high temperature ceramic phase (UHTC) and doped cerium oxide is proposed. UHTC usually exhibit extremely low mass diffusion rates and excellent thermomechanical properties for high temperature applications [2]. Gadolinium-doped ceria (CGO) presents unique processes at low oxygen partial pressure (pO2 < 10-12 atm) and high temperatures (T > 800 Ā°C) such as faster mass diffusion, which are not observed in conventional sintering under ambient air conditions. In CGO/Al2O3 composites the resulting effects driven by such mass diffusion are low viscosity flows and high reactivity between phases, indicated by the formation of CeAlO3[3]. In this work, a comparison is made between sintering CGO/Al2O3 under ambient air and reducing condition, focusing on densification, viscosity and the evolution of the microstructure. The redox process of CGO/Al2O3 is investigated using dilatometry, microscopy, and electrochemical impedance spectroscopy. The preliminary results evidenced that new phases with remarkable microstructure can be obtained at reducing atmosphere depending on the temperature of reoxidation during coolingArtigo IPEN-doc 24797 Thermochemical stability of zirconia-titanium nitride as mixed ionic-electronic composites2018 - SILVA, P.S.M.; ESPOSITO, V.; MARANI, D.; FLORIO, D.Z. de; MACHADO, I.F.; FONSECA, F.C.Dense zirconia (8% molar yttria-stabilized ZrO2)-titanium nitride (TiN) composites are fabricated to obtain mixed ionic-electronic conducting ceramic systems with high degree of electronic and thermal conductivity. The composites are consolidated by spark plasma sintering (SPS), starting from pure powders of the pristine phases mixed in different ratios (TiN = 25, 50, 75āÆwt%). A careful optimization of the SPS conditions allows producing highly dense samples with no reaction between the phases or degradation by oxidation, thus maintaining the chemical integrity of the two phases. For all the composites, high electrical conductivity is attained. Samples exhibit metallic behavior, showing an unexpected percolation of TiN in the YSZ matrix for volume fraction ā¤āÆ25āÆwt% (27āÆvol%). Chemical degradation and electrical properties of the compounds were monitored under oxidative (air) and inert (Ar) atmosphere at high temperatures. The oxidation kinetics of the nitride phase was inhibited by the microstructure of the composite. The electrical properties of such composites were explored at high temperature to evaluate its application in electrochemical devices. As results, it is shown that electrical transport properties of the composite can be tuned by both the relative volume fraction of phases and controlled oxidative treatments. Adjusting such parameters different electric behaviors were observed ranging from predominant electronic conductors, to temperature-independent resistivity, and semiconducting.Artigo IPEN-doc 20730 Spark plasma sintering of yttria-stabilized zirconia/titanium nitride composites2015 - SILVA, PAULO S.M.; FONSECA, FABIO C.