Seal glass is essential and plays a crucial role in solid oxide fuel/electrolyzer cell performance and durability. A seal glass should have a combination of thermal, chemical, mechanical, and electrical properties in order to seal different cell components and stacks and prevent gas leakage. All the desired properties can simultaneously be obtained in a seal glass by suitable compositional design. In this dissertation, SrO-La₂O₃-A₂O₃-B₂O₃3-SiO₂ based seal glasses have been developed and composition-structure-property relationships have been investigated. B₂O₃ free SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass is the most suitable and its compatibility with the metallic interconnects and sealing performances have been evaluated. A seal glass should be stable for 5,000-40,000 hrs in the oxidizing and reducing atmospheres at 600-900°C but both the thermal and chemical stability is a persistent problem. The effect of Al₂O₃ on a SrO-La₂O₃-Al₂O₃-B₂O₃-SiO₂ based seal glass has been studied to improve the thermal properties, such as glass transition temperature, softening temperature and thermal expansion coefficient, and the thermal stability. Al₂O₃ improves the thermal stability but does not significantly affect the thermal properties of the seal glass. Comprehensive understanding of composition-structure-property relationships is needed to design a suitable seal glass. The thermal properties and stability of a borosilicate seal glass depend on the B2O3:SiO2 ratio in the composition. The role of B₂O₃:SiO₂ ratio on the glass network structure of the SrO-La₂O₃-Al₂O₃-B₂O₃-SiO₂ based seal glasses has been studied using Raman spectroscopy and nuclear magneto resonance spectroscopy. The thermal properties and thermal stability were correlated with the glass network structure and the calculated network connectivity. This study shows that the thermal properties degrade with increasing B₂O₃:SiO₂ ratio due to increase in the non-bridging oxygen and decrease in the network connectivity. High B₂O₃:SiO₂ ratio induces BO4 and SiO4 structural unit ordering, increases micro-heterogeneity, and subsequently degrades thermal stability. B₂O₃ free SrO-La₂O₃-Al₂O₃-SiO₂ seal glass shows the best combination of the thermal properties and thermal stability among the studied glasses. Nickel or nickel oxide is added into a seal glass to modify the thermal properties depending on the specific composition. The role of nickel as a network former or modifier and its effect on the thermal properties and thermal stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glasses have been investigated. Nickel is a modifier in this glass system and does not improve the thermal properties but degrades thermal stability by decreasing network connectivity and inducing micro-heterogeneity. The interconnect-seal glass interface stability is the most crucial for solid oxide fuel/electrolyzer cell. Crofer 22 APU and AISI 441 alloys are the preferred interconnects. The interfacial stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass with these alloys have been studied as a function of time (0-1000 hrs), temperature (700-850°C), atmospheres (air, argon, and H₂O/H₂) using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction analysis (XRD). Complementary analytical techniques such as wave length dispersive spectroscopy (WDS) and SEM of thin samples were also carried out for selected samples. This study shows good interfacial stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass with these alloys for the studied conditions. A suitable seal glass should be hermetic and withstand 100-1000 thermal cycles for practical application. Sealing performances of the SrO-La2O3-Al2O3-SiO2 based seal glass have been evaluated by pressure-leakage method. The seal glass is hermetic for at least 2000 hrs and withstands 100 thermal cycles. Overall, present work shows that the SrO-La₂O₃-Al₂O₃-SiO₂ based glass has all the desired properties and suitable for solid oxide fuel/electrolyzer cell seal. / Ph. D.

Made available in DSpace on 2014-12-17T14:06:53Z (GMT). No. of bitstreams: 1 ClawsioRCS_DISSERT.pdf: 4688648 bytes, checksum: dd0d723d2cc3d7de35608b8ed730a95b (MD5) Previous issue date: 2010-03-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 ? C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests. / As pilhas unit?rias de uma pilha a combust?vel de ?xido s?lido s?o separadas por meio de interconectores, que servem como contato el?trico entre as pilhas. A cromita de lant?nio (LaCrO3) tem sido o material mais utilizado como interconector nas pilhas a combust?vel de ?xido s?lido. A redu??o da temperatura de opera??o em torno de 800 ?C das pilhas a combust?vel de ?xido s?lido, tornou poss?vel o uso de interconectores met?licos como alternativa aos LaCrO3 cer?micos. Esses materiais apresentam vantagens em rela??o aos interconectores cer?micos tais como: alta condutividade t?rmica, el?trica, boa ductilidade, baixo custo, boas propriedades f?sicas e mec?nicas. Neste trabalho foram avaliadas as propriedades termomec?nicas do substrato met?lico e substrato met?lico recoberto com o filme de LaCrO3 via spray-pir?lise, com o objetivo de demonstrar a viabilidade da utiliza??o deste materiais como componente de uma pilha a combust?vel de ?xido s?lido. Os materiais foram caracterizados por meio de difra??o de raios-X, comportamento oxidativo, resist?ncia mec?nica, microscopia ?ptica e microscopia eletr?nica de varredura (MEV). A difra??o de raios-X comprovou a forma??o da fase LaCrO3 sobre o substrato met?lico e a identifica??o das fases formadas ap?s o ensaio oxidativo e resist?ncia mec?nica a alta temperatura.O comportamento oxidativo evidenciou o aumento da resist?ncia a oxida??o do substrato met?lico recoberto. Na resist?ncia mec?nica a flex?o do substrato met?lico recoberto, notou-se o aumento apenas na temperatura ambiente. A microscopia ?ptica (MO) fez uma avalia??o pr?via tanto do substrato met?lico e do filme de LaCrO3 recoberto sobre o substrato met?lico,que em compara??o com as micrografias obtidas por MEV. Com aux?lio do MEV comprovou a forma??o da camada de Cr2O3 sobre o substrato met?lico e a estabilidade do filme de LaCrO3 ap?s o ensaio oxidativo. Observando tamb?m o descolamento do filme de LaCrO3 ap?s ensaio mec?nico e a distribui??o dos principais elementos como: cromo, mangan?s, oxig?nio, lant?nio nas amostras que foram submetidas aos ensaios termo-mec?nicos

Made available in DSpace on 2014-12-17T14:07:21Z (GMT). No. of bitstreams: 1 ClawsioRCS_TESE.pdf: 6209957 bytes, checksum: 4a85a36be678a5c36d937dd4cb67fe7c (MD5) Previous issue date: 2014-04-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 ? C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 ?C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test / A cromita de lant?nio (LaCrO3) dopada tem sido o material mais utilizado como interconector nas pilhas a combust?vel de ?xido s?lido de alta temperatura(PaCOS-AT), possibilitando o empilhamento(stack) da PaCOS. A redu??o da temperatura de opera??o, em torno de 800 ?C, das pilhas a combust?vel de ?xido s?lido, tornou poss?vel o uso de interconectores met?licos como alternativa aos LaCrO3 cer?micos. Do ponto de vista pr?tico para o material ser forte candidato a interconector deve ter boas propriedades f?sicas e mec?nicas, como resist?ncia a ambientes oxidantes e redutores, f?cil fabrica??o e propriedades termo-mec?nicas adequadas. Por este motivo realizou-se um estudo sobre as propriedades fisico-mec?nicas de interconectores de La0,8Sr0,2Cr0,92Co0,08O3 cer?mico para PaCOS-AT obtido pelo m?todo da combust?o, como tamb?m sobre as propriedades termo-mec?nicas de interconectores met?licos (AISI 444) recobertos com La0,8Ca0,2CrO3 pela t?cnica de deposi??o por spray-pir?lise para Pilhas a combust?vel de temperatura intermediaria (PaCOS-TI). A La0,8Sr0,2Cr0,92Co0,08O3 foi caracterizada por meio de difra??o de raios X (DRX), densidade e porosidade, dureza Vickers (HV), resist?ncia mec?nica a flex?o na temperatura ambiente e a 900?C e microscopia eletr?nica de varredura (MEV). A difra??o de raios X comprovou a forma??o das fases LaCrO3 e CoCr2O4, dureza na ordem de 6 GPa e resist?ncia mec?nica a temperatura ambiente de 62 MPa do interconector cer?mico. A avalia??o das fases formadas no interconector met?lico recoberto com La0,8Ca0,2CrO3 tanto na deposi??o quanto ap?s o ensaio oxidativo foi realizado por DRX. O comportamento oxidativo evidenciou o aumento da resist?ncia a oxida??o do substrato met?lico recoberto por La0,8Ca0,2CrO3. Na resist?ncia mec?nica a flex?o do substrato met?lico recoberto, notou-se o aumento apenas na temperatura ambiente. Com aux?lio do MEV comprovou-se a forma??o das camadas de Cr2O3 e (Cr,Mn)3O4 sobre o substrato met?lico e confirmou-se a estabilidade do filme cer?mico de La0,8Ca0,2CrO3 ap?s o ensaio oxidativo

La technologie de l’électrolyse de la vapeur d’eau à haute température (EVHT) est unesolution alternative à la production d’hydrogène. Le principe est inversé à celui d’une pile àcombustible de type SOFC : on utilise la vapeur d’eau et de l’électricité afin de produire del’hydrogène. Une difficulté technique majeure repose sur la mise au point d’interconnecteursfonctionnant efficacement sur le long terme. Sur le plan électrique, l’interconnecteur doitprésenter une valeur de résistance de contact aux électrodes la plus faible possible, car elleaffecte directement le rendement de conversion électrochimique (eau en hydrogène) et peutpénaliser le procédé. Il ne doit donc pas présenter une cinétique d’oxydation élevée ni formerdes oxydes isolants électriquement. Sur le plan chimique, l’interconnecteur doit être résistantà l’oxydation sous atmosphère riche en oxygène côté anode et riche en vapeur d’eau côtécathode. De plus, le problème de la volatilisation des oxydes de chrome, qui peuvent diffuseret empoisonner les électrodes, déterminant ainsi une réduction de l’activité électrochimique etdes performances du « stack » sur des longues durées de fonctionnement, doit être réduit. Latempérature de fonctionnement comprise entre 700 et 900°C permet l’utilisationd’interconnecteurs métalliques, qui présentent l’avantage d’une mise en oeuvre plus facile etd’un coût plus faible par rapport aux interconnecteurs céramiques.Dans cette étude, deux matériaux ont été testés en tant qu’interconnecteurs pour lessystèmes EVHT : un acier ferritique chromino-formeur K41X et un alliage Fe-Ni-Co necontenant pas de chrome. Le comportement envers la corrosion à haute température et laconductivité électrique des deux alliages ont été évalués à 800°C sous un mélange 95%O2-5%H2O, pour le côté anodique, et 10%H2-90%H2O, pour le côté cathodique. Pour l’alliageK41X, l’effet de l’état initial de la surface des échantillons sur la nature des oxydes formés àhaute température sous mélange H2-H2O a été pris en compte, à travers une comparaison desalliages bruts de laminage avec des surfaces polies miroir. L’effet d’une pré-oxydation decourte durée à 800°C sur le comportement à haute température de l’alliage K41X brut deréception sous atmosphère H2-H2O a également été évalué. Mais, le travail le plus original decette étude a consisté à effectuer des essais de marquage à l’or et des marquages isotopiquessous mélange H216O-H218O, H2-D2O et D2-H2O. Ces tests ont permis d’étudier lesmécanismes responsables de la croissance de la couche de corrosion de l’alliage K41X brut deréception et poli miroir à 800°C sous atmosphère H2-H2O et d’évaluer le rôle de la vapeurd’eau et de l’hydrogène dans le mécanisme d’oxydation / The high temperature water vapour electrolysis offers a promising method for highlyefficient hydrogen production. It works as an inverse solid oxide fuel cell, using water vapourand electricity in order to produce hydrogen. A major technical difficulty related to hightemperature water vapour electrolysis (HTVE) is the development of interconnects workingefficiently on a long period. From the electrical point of view, the interconnect must have alow contact resistance with the electrodes. Indeed, it directly affects the electrochemicalconversion efficiency (water into hydrogen) and it can penalize the process. The interconnectmust present a slow oxidation kinetics and form as less as possible electrical insulatingoxides. From the chemical point of view, the interconnect has to be resistant against oxidationin an oxygen rich atmosphere (anode side) and water vapour rich atmosphere (cathode side).Moreover, the problem of the volatility of chromium oxide species, which might migrate andpoison the electrodes, leading to a decrease in their electrochemical activity and degradationof stack performance, over long-term operation, needs to be reduced. The operatingtemperature between 700°C and 900°C allows the use of metallic interconnects, which havehigher electrical and thermal conductivities, easier shaping and lower cost, with respect to theceramic materials.In this study, two materials were tested as interconnects for the HTVE systems: a ferriticchromia-forming alloy, the K41X, and a Fe-Ni-Co alloy, which does not contain chromium.High temperature corrosion behaviour and electrical conductivity were tested in both anode(95%O2-5%H2O) and cathode (10%H2-90%H2O) atmospheres at 800°C. Moreover, for theK41X alloy, the effect of the initial surface state of the samples on the chemical nature of theoxides formed at 800°C in H2-H2O atmosphere was evaluated, by comparing as received andmirror polished surfaces. The effect of a short-term air preoxidation at 800°C on the hightemperature behaviour of the K41X as received sample in H2-H2O atmosphere was tested.The most original part of this study consisted in the investigation of the oxidation mechanismsof both as received and mirror polished K41X samples at 800°C in H2-H2O atmosphere bymeans of marking experiments using Au and isotopes (H216O-H218O mixture). Moreover,marking tests using H2-D2O and D2-H2O were carried out, in order to further investigate therole of hydrogen and water vapour in the oxidation mechanism