Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (> 50 wt.%). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications.

Precursor scavenging of the resistive grain-boundary phase in 8 mol% yttria-stabilized zirconia: Effect of trace concentrations of SiO2

The influence that trace concentrations Of SiO2 have on improving grain-boundary conduction via precursor scavenging using additional heat treatment at 1200 degreesC for 40 h before sintering was investigated. At a SiO2-impurity level (SIL) less than or equal to 160 ppm by weight, the grain-boundary resistivity (p(gb)) decreased to 20% of its value, while no improvement in grain-boundary conduction was found at a SIL greater than or equal to 310 ppm. The correlation between the resistance per unit grain-boundary area, p(gb), and average grain size indicated that the inhomogeneous distribution of the siliceous phase in the sample with a SIL greater than or equal to 310 ppm. hampered the scavenging reaction.

Surface roughness and hardness of yttria stabilized zirconia (Y-TZP) after 10 years of simulated brushing

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The influence of photon excitation and proton irradiation on the luminescence properties of yttria stabilized zirconia doped with praseodymium ions

Lanthanide doped zirconia based materials are promising phosphors for lighting applications. Transparent yttria stabilized zirconia fibres, in situ doped with Pr3+ ions, were grown by the laser floating zone method. The single crystalline doped fibres were found to be homogeneous in composition and provide an intense red luminescence at room temperature. The stability of this luminescence due to transitions between the 1D2 → 3H4 multiplets of the Pr3+ ions (intra-4f2 configuration) was studied by photo- and iono-luminescence. The evolution of the red integrated photoluminescence intensity with temperature indicates that the overall luminescence decreases to ca. 40% of the initial intensity at 14 K when heated to room temperature (RT). RT analysis of the iono-luminescence dependence on irradiation fluence reveals a decrease of the intensity (to slightly more than ∼60% of the initial intensity after 25 min of proton irradiation exposure). Nevertheless the luminescence intensity saturates at non-zero values for higher irradiation fluences revealing good potential for the use of this material in radiation environments.

Scavenging of siliceous grain-boundary phase of 8-mol%-ytterbia-stabilized zirconia without additive

The grain-boundary conductivity (sigma (gb),) of 8-mol%-ytterbiastabilized zirconia increased markedly with heat treatment between 1000 degrees and 1300 degreesC with a slow heating rate (0.1 degreesC/min) before sintering. The extent of the sigma (gb) improvement was the same or larger than that via Al2O3 addition. The heat treatment did not affect the grain-interior conduction when sintered at 1600 degreesC, while Al2O3-derived scavenging significantly did, given the larger increment of total conductivity in the heat-treated sample. The formation of a silicon-containing phase in a discrete form was suggested as a possible route of scavenging the resistive phase from the correlation between average grain size and sigma (gb).

Determinacion de las propiedades mecanicas y mecanismos de fractura de electrolitos soportados de YSZ y GDC mediante ensayos de indentacion instrumentada

El objetivo del presente trabajo es evaluar las propiedades mecánicas, así como los diferentes mecanismos de fractura activados mediante ensayos de indentación instrumentada, de electrolitos basados en circona estabilizada con itria ("yttria stabilized zirconia",YSZ) y ceria dopada con gadolinia ("gadolinia doped ceria", GDC), para pilas de combustible de óxido sólido, SOFCs. Ambos materiales, con un espesor final de 200 ¿m, se conformaron mediante prensado uniaxial a 500 MPa y se sinterizaron a 1400ºC. Propiedades mecánicas tales como la dureza (H) y el módulo de Young (E) han sido estudiadas a diferentes profundidades de penetración utilizando el algoritmo de Oliver y Pharr.

Mixed ionic-electronic YSZ/Ni composite for SOFC anodes with high electrical conductivity

The preparation of the ZrO(2):8 mol % Y(2)O(3)/NiO (YSZ/NiO) composites by a modified liquid mixture technique is reported. Nanometric NiO particles dispersed over the yttria-stabilized zirconia (YSZ) were prepared, resulting in dense sintered specimens with no solid solution formation between the oxides. Such a feature allowed for the electrical characterization of the composites in a wide range of relative volume fraction, temperature, and oxygen partial pressure. The main results indicate that the composites have high electrical conductivity, and the transport properties in these mixed ionic-electronic (MIEC) composites are strongly dependent on the relative volume fraction of the phases, microstructure, and temperature. These parameters should hence be taken into consideration for the optimized design of MIEC composites for electrochemical applications. In this context, the composite was reduced under H(2) for the preparation of high-conductivity YSZ/Ni cermets for use as solid oxide fuel cell anode material with relatively low metal content. (c) 2005 the Electrochemical Society. [DOI:10.1149/1.2149312] All rights reserved.

Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo2O5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15m thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing anda Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm−2 at 700◦C and ca. 250 mW cm−2 at 800◦C are reported for this standard configuration using 5% of H2 in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm−2 at 700◦C and ca. 500 mW cm−2 at 800◦C in this configuration were achieved.

An Experimental Study of Submerged Entry Nozzles (SEN) Focusing on Decarburization and Clogging

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Reação de redução de oxigênio sobre perovskitas La1-xSrxFeyCo1-yO3-δ, para células a combustível de óxido sólido (SOFC)

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Influence of particle morphology on nanostructural feature and conducting property in Sm-doped CeO2 sintered body

Doped ceria (CeO2,) compounds are fluorite type oxides, which show oxide ionic conductivity higher than yttria stabilized zirconia (YSZ), in oxidizing atmospheres. As a consequence of this, considerable interest has been shown in application of these materials for 'low (500-650 degreesC)' or 'intermediate (650-800 degreesC)' temperature operation, solid oxide fuel cells (SOFCs). In this study, the authors prepared two kinds of nanosize Sm-doped CeO2 particles with different morphologies: one type was round and the other was elongated. Processing these powders with different morphology produced dense materials with very different ionic conducting properties and different nanoscale microstructures. Since both particles are very fine and well dispersed, sintered bodies with high density (relative density >95% of theoretical) could be prepared using both types of powder particles. The electrical conductivity of sintered bodies prepared from these powders with different starting morphologies was very different. Materials prepared from particles having a round shape were much higher than those produced using powders with an elongated morphology. Measured activation energies of the corresponding sintered samples showed a similar trend; round particles (60 kJ/mol), elongated particles (74 kJ/mol). While X-ray diffraction (XRD) profiles of these sintered materials were identical, diffuse scatter was observed in the back.-round of selected area electron diffraction pattern recorded from both sintered bodies. This indicated an underlying structure that appeared to have been influenced by the processing technology. Detailed observation using high-resolution transmission electron microscopy (HR-TEM) revealed that the size of microdomain with ordering of cations in the sintered body made from round shape particles was much smaller than that of the sintered body made from elongated particles. Accordingly, it is concluded that the morphology of doped CeO2 powders strongly influenced the microdomain size and electrolytic properties in the doped CeO2 sintered body. (C) 2004 Elsevier B.V. All rights reserved.

Development of the Oxide Ion Conductor Na0.5Bi0.5TiO3 (NBT) for Solid Oxide Cells

Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material with potential to replace lead zirconate titanate (PZT),1 however high leakage conductivity for the material has been widely reported.2 Through a combination of Impedance Spectroscopy (IS), O2- ion transference (EMF) number experiments and O18 tracer diffusion measurements, combined with Time-of-flight Secondary Ion Mass Spectrometry (TOFSIMS), it was identified that this leakage conductivity was due to oxygen ion conductivity. The volatilization of bismuth during synthesis, causing oxygen vacancies, is believed to be responsible for the leakage conductivity.3 The oxide-ion conductivity, when doped with magnesium, exceeds that of yttria-stabilized zirconia (YSZ) at ~500 °C,3 making it a potential electrolyte material for Intermediate Temperature Solid Oxide Cells (ITSOCs). Figure 1 shows the comparison of bulk oxide ion conductivity between 2 at.% Mg-doped NBT and other known oxide ion conductors.

As part of the UK wide £5.7m 4CU project, research has concentrated on trying to develop NBT for use in Intermediate Temperature Solid Oxide Cells (ITSOCS). With the aim of achieving mixed ionic and electronic conduction, transition metals were chemically doped on to the Ti-site. A range of experimental techniques was used to characterize the materials aimed at investigating both conductivity and material structure (Scanning Electron Microscopy (SEM), IS, X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS)). The potential for NBT as an ITSOC material, as well as the challenges of developing the material, will be discussed.

(1) Takenaka T. et al. Jpn. J. Appl. Phys 1999, 30, 2236.

(2) Hiruma Y. et al. J. Appl. Phys 2009, 105, 084112.

(3) Li. M. et al. Nature Materials 2013, 13, 31.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation