Studio ed ottimizzazione di processi per la produzione di membrane ceramiche per la separazione di idrogeno

Questa tesi descrive l’attività scientifica svolta presso l’istituto CNR-ISTEC di Faenza. Lo scopo è stato lo studio e l’ottimizzazione del processo per la realizzazione di una membrana ceramica permselettiva all’idrogeno usufruibile in applicazioni industriali. Grazie alle prove effettuate è stata possibile la realizzazione tramite colaggio su nastro dei due strati ceramici che formano la membrana: un supporto poroso e un film sottile e denso. I nastri, dopo essiccamento, sono stati tagliati con la geometria desiderata, impilati uno sull’altro, termocompressi e sinterizzati. L’attività svolta ha permesso l’ingegnerizzazione di una membrana ad elevato contenuto tecnologico con le proprietà necessarie per poter essere impiegata in un processo di purificazione di idrogeno più semplice, efficiente ed economico rispetto a quelli utilizzati fino ad ora.

Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0.2Sr0.7TiO3-Ni/YSZ functional gradient anode supported solid oxide fuel cell

The ability to directly utilize hydrocarbons and other renewable liquid fuels is one of the most important issues affecting the large scale deployment of solid oxide fuel cells (SOFCs). Herein we designed La_0.2Sr_0.7TiO₃-Ni/YSZ functional gradient anode (FGA) supported SOFCs, prepared with a co-tape casting method and sintered using the field assisted sintering technique (FAST). Through SEM observations, it was confirmed that the FGA structure was achieved and well maintained after the FAST process. Distortion and delamination which usually results after conventional sintering was successfully avoided. The La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs showed a maximum power density of 600mWcm^-2 at 750°C, and was stable for 70h in CH₄. No carbon deposition was detected using Raman spectroscopy. These results confirm the potential coke resistance of La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs.

Estudo e desenvolvimento de filmes espessos de CeO2 obtidos por tape casting

Tape Casting proved to be an effective method for the production of thick films of CeO2 pure and doped with La. For this study, the nanoparticles used to form the slurry were synthesizes by the H-M method, at 100°C for 8 minutes, using KOH mineralizer. The slurry was made in aqueous solvent, requiring optimal control of surroundings conditions so that the produced tape has conditions to be studied. However, there's no toxicity or flammability in the film made by such solvent, being pleasing to the environment. The structural, optical and electrical properties of the films obtained by the Tape Casting process were studied by the methods of X-ray diffraction, scanning electron microscopy, specific surface area, Ultraviolet-visible spectroscopy and voltage-current measures, varying the electric field and frequency. From the results obtained by laboratory experiments, based on the literature, it was possible to reveal and understand some CeO2 features pure and doped with La

Estudo e desenvolvimento de filmes espessos de CeO2 obtidos por tape casting

Tape Casting proved to be an effective method for the production of thick films of CeO2 pure and doped with La. For this study, the nanoparticles used to form the slurry were synthesizes by the H-M method, at 100°C for 8 minutes, using KOH mineralizer. The slurry was made in aqueous solvent, requiring optimal control of surroundings conditions so that the produced tape has conditions to be studied. However, there's no toxicity or flammability in the film made by such solvent, being pleasing to the environment. The structural, optical and electrical properties of the films obtained by the Tape Casting process were studied by the methods of X-ray diffraction, scanning electron microscopy, specific surface area, Ultraviolet-visible spectroscopy and voltage-current measures, varying the electric field and frequency. From the results obtained by laboratory experiments, based on the literature, it was possible to reveal and understand some CeO2 features pure and doped with La

Desenvolvimento de cerâmicas texturizadas de titanato de bismuto puro e dopado com nióbio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Celle ad Ossidi Solidi per Elettrolisi ad Alta Temperatura

Lo scopo di questa tesi è stato la produzione di un elettrolizzatore ad ossidi solidi (SOEC) mediante tecniche economiche e facilmente industrializzabili. Fondamentale a questo scopo è stata la realizzazione di una semicella costituita da un anodo poroso a base di La0.8Sr0.2MnO3-Ce0.8Gd0.2O2-δ (LSM-GDC) ed un elettrolita denso a base di Ce0.8Gd0.2O2-δ (GDC). Le tecniche utilizzate per la produzione di questo sistema sono state il colaggio su nastro e la serigrafia. Anche se generalmente, le celle SOEC vengono prodotte catodo supportate, in questo studio, l’elemento supportante scelto è stato l’anodo poiché questo garantisce una migliore stabilità meccanica all’intera cella. Tale substrato è stato ottenuto mediante colaggio su nastro accoppiato con un metodo innovativo di sinterizzazione denominato sinterizzazione reattiva, processo che prevede la formazione della fase di interesse durante un unico trattamento termico di eliminazione degli additivi organici e consolidamento del manufatto finale. La membrana elettrolitica per l’ottenimento del bilayer anodo-elettrolita, è stata prodotta mediante sia serigrafia che colaggio su nastro. L’accurato studio dell’evoluzione di fase della polvere anodica, l’ottimizzazione della sospensione per colaggio su nastro e dei trattamenti termici hanno permesso l’ottenimento di anodi (fino a dimensioni di 10x10 cm2). Lo studio dei profili di sinterizzazione delle polveri anodica ed elettrolitica e dell’influenza della tecnica di formatura sulla sinterabilità dei layer elettrolitici prodotti hanno inoltre permesso l’ottenimento di una semicella planare costituita da un elettrodo poroso ed una membrana elettrolitica densa adatte per applicazioni SOEC.

Fabrication and characterization of SSZ tape cast electrolyte-supported solid oxide fuel cells

A 10 mol%Sc₂O₃, 1 mol%CeO₂ stabilized-ZrO₂ (SSZ) powder was successfully prepared using the sol-gel method. Subsequent SSZ electrolyte pellets were prepared by tape casting technique and sintered at 1400 °C, 1450 °C, 1500 °C, 1550 °C and 1600 °C. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). SSZ showed a pure cubic phase after sintering, the grain size of SSZ increased with the increase of sintering temperature. The SSZ sintered at 1550 °C showed the highest ion conductivity. The maximum power densities of Ni-SSZ/SSZ/La_0.8Sr_0.2MnO_3-δ (LSM)-SSZ single cells sintered at 1550 °C were 0.18, 0.36, 0.51 and 0.72 W cm^-2 at 650, 700, 750 and 800 °C, respectively. The polarization resistance (R_p) of the single cell attained 0.201 Ω cm² at 800 °C.

Alkaline-earth aluminosilicate-based glass and glass-ceramic sealants for functional applications

The planar design of solid oxide fuel cell (SOFC) is the most promising one due to its easier fabrication, improved performance and relatively high power density. In planar SOFCs and other solid-electrolyte devices, gas-tight seals must be formed along the edges of each cell and between the stack and gas manifolds. Glass and glass-ceramic (GC), in particular alkaline-earth alumino silicate based glasses and GCs, are becoming the most promising materials for gas-tight sealing applications in SOFCs. Besides the development of new glass-based materials, new additional concepts are required to overcome the challenges being faced by the currently existing sealant technology. The present work deals with the development of glasses- and GCs-based materials to be used as a sealants for SOFCs and other electrochemical functional applications. In this pursuit, various glasses and GCs in the field of diopside crystalline materials have been synthesized and characterized by a wide array of techniques. All the glasses were prepared by melt-quenching technique while GCs were produced by sintering of glass powder compacts at the temperature ranges from 800−900 ºC for 1−1000 h. Furthermore, the influence of various ionic substitutions, especially SrO for CaO, and Ln2O3 (Ln=La, Nd, Gd, and Yb), for MgO + SiO2 in Al-containing diopside on the structure, sintering and crystallization behaviour of glasses and properties of resultant GCs has been investigated, in relevance with final application as sealants in SOFC. From the results obtained in the study of diopside-based glasses, a bilayered concept of GC sealant is proposed to overcome the challenges being faced by (SOFCs). The systems designated as Gd−0.3 (in mol%: 20.62MgO−18.05CaO−7.74SrO−46.40SiO2−1.29Al2O3 − 2.04 B2O3−3.87Gd2O3) and Sr−0.3 (in mol%: 24.54 MgO−14.73 CaO−7.36 SrO−0.55 BaO−47.73 SiO2−1.23 Al2O3−1.23 La2O3−1.79 B2O3−0.84 NiO) have been utilized to realize the bi-layer concept. Both GCs exhibit similar thermal properties, while differing in their amorphous fractions, revealed excellent thermal stability along a period of 1,000 h. They also bonded well to the metallic interconnect (Crofer22APU) and 8 mol% yttrium stabilized zirconium (8YSZ) ceramic electrolyte without forming undesirable interfacial layers at the joints of SOFC components and GC. Two separated layers composed of glasses (Gd−0.3 and Sr−0.3) were prepared and deposited onto interconnect materials using a tape casting approach. The bi-layered GC showed good wetting and bonding ability to Crofer22APU plate, suitable thermal expansion coefficient (9.7–11.1 × 10–6 K−1), mechanical reliability, high electrical resistivity, and strong adhesion to the SOFC componets. All these features confirm the good suitability of the investigated bi-layered sealant system for SOFC applications.

Electrical and Optical Properties of Conductive and Transparent ITO@PMMA Nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrical Properties of Textured Niobium-Doped Bismuth Titanate Ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of ITO@PMMA composites by transmission electron microscopy

ITO nanowires were synthesized by carbothermal reduction process, using a co-evaporation method, and have controlled size, shape, and chemical composition. The electrical measurements of nanowires showed they have a resistance of about 102 Ω. In order to produce nanocomposites films, nanowires were dispersed in toluene using an ultrasonic cleaner, so the PMMA polymer was added, and the system was kept under agitation up to obtain a clear suspension. The PMMA polymer was filled with 1, 2, 5 and 10% in weight of nanowires, and the films were done by tape casting. The results showed that the electrical resistance of nanocomposites changed by over 7 orders of magnitude by increasing the amount of filler, and using 5 wt% of filler the composite resistance decreased from 1010 Ω to about 104 Ω, which means that percolation threshold of wires occurred at this concentration. This is an interesting result once for nanocomposites filled with ITO nanoparticles is necessary about 18% in weight to obtain percolation. The addition of filler up to 10 wt% decreased the resistance of the composite to 103 Ω, which is a value close to the resistance of wires. The composites were also analyzed by transmission electron microscopy (TEM), and the TEM results are in agreement with the electrical ones about percolation of nanowires. These results are promising once indicates that is possible to produce conductive and transparent in the visible range films by the addition of ITO nanowires in a polymeric matrix using a simple route. © 2011 Materials Research Society.

Multilaminati piezoelettrici a gradiente funzionale

Aim of this thesis was the production of porosity-graded piezoelectric ceramics for ultrasonic applications by tape casting and screen printing. The study and optimization of each single step of the tape casting process allowed to produce flat and crack-free multilayers of Pb0.988(Zr0.52Ti0.48)0.976Nb0.024O3 (PZTN) of uniform and graded porosity. The multilayers of thickness ranging between 400 and 800 µm were produced stacking optimized green layers with different amount of pore former. The functionally graded materials showed porosity ranging between 10 and 30% with piezoelectric properties suitable for the specific ultrasonic applications. Screen printing inks of PZTN for deposition onto four different substrates were studied and optimized. Thick films with thickness ranging between 4 and 20 µm were produced tailoring the screen printing parameters and number of depositions.

Sviluppo di un sistema integrato innovativo per la contemporanea produzione e separazione di H2 ultrapuro, attraverso oxy-reforming, water-gas shift e membrane al Pd

Il presente lavoro di tesi si è focalizzato sullo studio e sulla ottimizzazione di un sistema integrato, che utilizzi la reazione di oxy-reforming del metano al fine di produrre syngas che venga trattato attraverso la water-gas shift al fine di abbattere il contenuto di CO e al tempo stesso aumentare la resa in H2. Con l’obiettivo di ottenere H2 ad elevata purezza (>99%) da poter essere inviato direttamente a celle a combustible ed in impianti di piccola taglia con possibile delocalizzazione della produzione industriale di energia elettrica e termica “pulita”, la miscela reale uscente dal processo di oxy-reforming è stata processata tramite successiva water-gas shift direttamente all’interno di una membrana ceramica al Pd selettiva nella separazione di H2. L’innovativià di questo progetto di studio è data da diversi parametri quali: 1) l’impiego dell’oxy-reforming in alternativa al normale steam-reforming del CH4, che permette di condurre il processo a temperature decisamente inferiori (700-750°C), utilizzando un minor quantitativo di vapore (S/C = 0.7); 2) l’utilizzo di due nuove formulazioni di catalizzatore di WGS per alte temperature, capace di operare in un unico stadio conversioni di CO ottenibili industrialmente solo attraverso i convenzionali due due stadi di reazione (e due diverse formulazioni di catalizzatori a base di Fe/Cr e Cu); 3) l’utilizzo di supporti ceramici con membrana a base di Pd, capaci di ospitare al loro interno un catalizzatore eterogeneo per la reazione di WGS a 400°C, rendendo quindi possibile la produzione e contemporanea separazione di H2 con un ulteriore effetto positivo poiché la membrana rimuovendo H2 dalla zona di reazione favorisce il superamento dell’equilibrio termodinamico per la conversione del CO, abbassandone il contenuto nel flusso uscente dei gas reazione e rendendo non più necessari sistemi aggiuntivi di separazione quali PSA o PROXY.

Effect of composition, sonication and pressure on the rate capability of 5 V-LiNi0.5Mn1.5O4 composite cathodes

Positive composite electrodes having LiNi0.5Mn1.5O4 spinel as active material, a blend of graphite and carbon black for increasing the electrode electrical conductivity and either polyvinyldenefluoride (PVDF) or a blend of PVDF with a small amount of Teflon® (1 wt%) for building up the electrode. They have been processed by tape casting on an aluminum foil as current collector using the doctor blade technique. Additionally, the component blends were either sonicated or not, and the processed electrodes were compacted or not under subsequent cold pressing. Composites electrodes with high weight, up to 17 mg/cm2, were prepared and studied as positive electrodes for lithium-ion batteries. The addition of Teflon® and the application of the sonication treatment lead to uniform electrodes that are well-adhered to the aluminum foil. Both parameters contribute to improve the capacity drained at high rates (5C). Additional compaction of the electrode/aluminum assemblies remarkably enhances the electrode rate capabilities. At 5C rate, remarkable capacity retentions between 80% and 90% are found for electrodes with weights in the range 3–17 mg/cm2, having Teflon® in their formulation, prepared after sonication of their component blends and compacted under 2 tonnes/cm2.

Relationship between residual stresses and mechanical behavior in ceramic composites

En este trabajo, materiales de tipo alúmina/Y-TZP (ZrO2 tetragonal, estabilizada con 3 mol. % Y2O3), como sistema cerámico popular por sus mejoradas propiedades mecánicas en comparación con las cerámicas de alúmina puras, han sido estudiados en términos de propiedades mecánicas y tensiones residuales. El novedoso método de colado en cinta, consistente en el apilamiento de cintas de cerámica verde a temperatura ambiente y el uso de bajas presiones, se ha escogido para la presente investigación con el fin de poder aprovechar al máximo el futuro desarrollo de materiales laminados de alúmina-óxido de circonio. Se han determinado las propiedades de los materiales obtenidos por este nuevo método de procesamiento comparándolas con las de los materiales obtenidos por “slip casting”, con el fin de analizar si el método propuesto afecta a la microestructura y, por tanto, a las propiedades mecánicas y tensiones residuales propias de estos materiales. Para analizar la idoneidad del proceso de fabricación, utilizado para evitar la presencia de discontinuidades en las intercaras entre las láminas así como otros fenómenos que puedan interferir con las propiedades mecánicas, se estudiaron materiales cerámicos con la misma composición en cintas. Por otra parte también se analizó el efecto de la adición de óxido de circonio sobre la aparición de tensiónes residuales en cerámicas Al2O3/Y-TZP, teniendo en cuenta su notable influencia sobre las propiedades microestructurales y mecánicas de los materiales, así como el requisito de co-sinterización de capas con diferentes materiales compuestos en materiales laminados. La caracterización del material incluye la determinación de la densidad, el análisis de la microestructura, la obtención de las propiedades mecánicas (módulo de elasticidad, dureza, resistencia a la flexión y tenacidad de fractura) así como de las tensiones residuales. En combinación con otros métodos de medida tradicionales, la nanoindentación también se empleó como una técnica adicional para la medida del módulo de elasticidad y de la dureza. Por otro lado, diferentes técnicas de difracción con neutrones, tanto las basadas en longitud de onda constante (CW) como en tiempo de vuelo (TOF), han sido empleadas para la medición fiable de la deformación residual a través del grosor en muestras a granel. Las tensiones residuales fueron determinadas con elevada precisión, aplicando además métodos de análisis apropiados, como por ejemplo el refinamiento de Rietveld. Las diferentes fases en cerámicas sinterizadas, especialmente las de zirconia, se examinaron con detalle mediante el análisis de Rietveld, teniendo en cuenta el complicado polimorfismo del Óxido de Zirconio (ZrO2) así como las posibles transformaciones de fase durante el proceso de fabricación. Los efectos del contenido de Y-TZP en combinación con el nuevo método de procesamiento sobre la microestructura, el rendimiento mecánico y las tensiones residuales de los materiales estudiados (Al2O3/Y-TZP) se resumen en el presente trabajo. Finalmente, los mecanismos de endurecimiento, especialmente los relacionados con las tensiones residuales, son igualmente discutidos. In present work, Alumina/Y-TZP (tetragonal ZrO2 stabilized with 3 mol% Y2O3) materials, as an popular ceramic system with improved mechanical properties compared with the pure alumina ceramics, have been studied in terms of mechanical properties and residual stresses. The novel tape casting method, which involved the stacking of green ceramics tapes at room temperature and using low pressures, is selected for manufacturing and investigation, in order to take full advantage of the future development of alumina-zirconia laminated materials. Features of materials obtained by the new processing method are determined and compared with those of materials obtained by conventional slip casting in a plaster mold, in order to study whether the proposed method of processing affects microstructure and thereby the mechanical properties and residual stresses characteristics of materials. To analyse the adequacy of the manufacturing process used to avoid the presence of discontinuities at the interfaces between the sheets and other phenomena that interfere with the mechanical properties, ceramic materials with the same composition in tapes were investigated. Moreover, the effect of addition of zirconia on residual stress development of Al2O3/Y-TZP ceramics were taken into investigations, considering its significantly influence on the microstructure and mechanical properties of materials as well as the requirement of co-sintering of layers with different composites in laminated materials. The characterization includes density, microstructure, mechanical properties (elastic modulus, hardness, flexure strength and fracture toughness) and residual stresses. Except of the traditional measurement methods, nanoindentation technique was also used as an additional measurement of the elastic modulus and hardness. Neutron diffraction, both the constant-wavelength (CW) and time-of-flight (TOF) neutron diffraction techniques, has been used for reliable through-thickness residual strain measurement in bulk samples. Residual stresses were precisely determined combined with appropriate analysis methods, e.g. the Rietveld refinement. The phase compositions in sintered ceramics especially the ones of zirconia were accurately examined by Rietveld analysis, considering the complex polymorph of ZrO2 and the possible phase transformation during manufacturing process. Effects of Y-TZP content and the new processing method on the microstructure, mechanical performance and residual stresses were finally summarized in present studied Al2O3/Y-TZP materials. The toughening mechanisms, especially the residual stresses related toughening, were theoretically discussed.