5th International Conference on Nanomaterials Science and Mechanical Engineering

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Corrosão e inibição de corrosão em combinações multi-materiais

Modern high-strength but environmentally friendly, fuel-efficient and weight-optimized designs vital to the aeronautical and transport industries have resulted in the multi-material concept in which a wide range of materials are employed to exploit the various desirable mechanical and physical properties. These multi-material design concepts are susceptible to corrosion as the chemical and electrochemical properties of their constituent materials can vary widely. Since current corrosion mitigation strategies are not focused on these multi-material systems, there is an urgent need to understand the mechanism of the corrosion processes operative in these multi-material assemblies and develop suitable multi-material corrosion mitigation solutions in tandem with the increasing design trend towards multi-material structures. This work has focused on understanding the mechanism of multi-material corrosion in two multi-material systems that are of relevance to the aeronautical and transport industries; Al - Cu - CFRP (carbon fiber reinforced polymers) and Zn - Fe - CFRP galvanic systems respectively. On the basis of the insights obtained, appropriate multi-material corrosion mitigation options using inhibitors are to be identified and verified at the laboratory scale. The thesis objectives have been pursued by an incremental escalation technique in which the five individual materials constituting the two multi-material galvanic systems were first studied at the macro-scale in quiescent 50 mM NaCl solutions with and without inhibitors. Particularly, CFRP the only non-metallic material used was extensively studied with a view to understanding its deleterious electrochemical action as an efficient cathode when coupled to metals and how to mitigate it. Next technologically relevant dual material couples most relevant to the two galvanic systems were studied at the macro- and micro-scales, on the premise that inhibitors efficient at mitigating galvanic corrosion in these simpler components (Al - CFRP, Al - Cu, and Cu - CFRP for the Al - Cu - CFRP galvanic system) and (Fe - CFRP, Zn - CFRP, and Zn - Fe for the Zn - Fe - CFRP galvanic system) are prone to be effective for an entire multi-material system. Finally, promising inhibitors identified from dual material galvanic studies are tested on the multi-material combinations leading to identification of efficient multi-material corrosion inhibitors for both the Al - Cu - CFRP and Zn - Fe - CFRP multi-material combinations. The results demonstrate better understanding of the electrochemical behaviour of CFRP under cathodic polarization on galvanic coupling with metals and potential strategies to suppressing its ability to support cathodic reactions, and successful identification of potential inhibitors for mitigating multi-material corrosion in both systems. On the basis of results obtained in this work a scheme for monitoring degradation of CFRP was postulated as well as plausible mechanism(s) of multi-material corrosion and multi-material corrosion inhibition in Al - Cu - CFRP and Zn - Fe - CFRP multi-material galvanic systems, respectivelyOs projectos mais recentes de veículos usados pelas indústrias aeronáutica e dos transportes combinam alta resistência, baixo peso, consumo eficiente de combustível e reduzido impacto ambiental, para o que juntam no mesmo desenho materiais muito diversos. A corrosão destas combinações multi-materiais pode ser acelerada quando se unem materiais com propriedades químicas e electroquímicas bastante diferentes. Como as estratégias actuais de mitigação da corrosão não focam sistemas multi-materiais, há a necessidade urgente em caracterizar os mecanismos da corrosão nestes novos sistemas a fim de desenvolver soluções eficazes para a sua prevenção. Este trabalho centrou-se na compreensão dos mecanismos da corrosão de dois sistemas multimateriais com relevância para as indústrias aeronáutica e dos transportes: Al - Cu - CFRP (polímeros reforçado com fibra de carbono) e Zn - Fe - CFRP, respectivamente. Com base nos resultados obtidos procurou-se identificar, à escala laboratorial, inibidores de corrosão eficazes. Começou-se por estudar separadamente cada um dos cinco materiais constituintes das combinações multi-materiais, em solução aquosa NaCl 50 mM com e sem inibidores de corrosão. O CFRP, o único material não metálico, foi estudado extensivamente para caracterizar a sua acção electroquímica como cátodo, pois esta torna-se prejudicial quando o CFRP está ligado a metais. Estudou-se também formas de minimizar a reacção catódica no CFRP e a corrosão dos outros metais. O passo seguinte foi o estudo de pares desses materiais à micro e macro-escala admitindo que os inibidores de corrosão capazes de reduzir a corrosão galvânica nestes sistemas simples (Al - CFRP, Al - Cu, e Cu - CFRP para o sistema galvânico Al - Cu - CFRP) e (Fe - CFRP, Zn - CFRP, e Zn - Fe para o sistema Zn - Fe - CFRP) serão também eficazes na protecção da estrutura multi-material real. Por fim os inibidores mais eficientes foram estados para as combinações multi-marieriais completas, Al - Cu - CFRP e Zn - Fe - CFRP. Os resultados obtidos trazem uma melhor compreensão do comportamento electroquímico do CFRP quando sujeito a polarização catódica ou quando ligado galvanicamente a vários metais. Os resultados apresentam também estratégias possíveis para impedir o processo catódico à superfície do CFRP. Identificou-se ainda vários compostos com a capacidade de inibir a corrosão nos sistemas Al - Cu - CFRP e Zn - Fe - CFRP. Como resultado do trabalho realizado para esta Tese, desenvolveu-se um procedimento para monitorização da degradação do “plástico” reforçado com fibra de carbono (CFRP). Propõem-se também mecanismos para a corrosão e inibição em sistemas multi-material como por exemplo, Al - Cu - CFRP e Zn - Fe - CFRPPrograma Doutoral em Ciência e Engenharia de Materiai

Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Applications

[EN] The rapid increasing of the population in combination with the emergence of new energy-consuming technologies has risen worldwide total energy consumption towards unprecedent values. Furthermore, fossil fuel reserves are running out very quickly and the polluting greenhouse gases emitted during their utilization need to be reduced. In this scenario, a few alternative energy sources have been proposed and, among these, proton exchange membrane (PEM) fuel cells are promising. Recently, polybenzimidazole-based polymers, featuring high chemical and thermal stability, in combination with fillers that can regulate the proton mobility, have attracted tremendous attention for their roles as PEMs in fuel cells. Recent advances in composite membranes based on polybenzimidazole (PBI) for high temperature PEM fuel cell applications are summarized and highlighted in this review. In addition, the challenges, future trends, and prospects of composite membranes based on PBI for solid electrolytes are also discussed.The authors acknowledge the Spanish Ministerio de Economía y Competitividad (MINECO) for the financial support under the project ENE/2015-69203-R.Escorihuela, J.; Olvera-Mancilla, J.; Alexandrova, L.; Del Castillo, LF.; Compañ Moreno, V. (2020). Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Applications. Polymers. 12(9):1-41. https://doi.org/10.3390/polym12091861S141129Kraytsberg, A., & Ein-Eli, Y. (2014). Review of Advanced Materials for Proton Exchange Membrane Fuel Cells. Energy & Fuels, 28(12), 7303-7330. doi:10.1021/ef501977kLi, Q., Jensen, J. O., Savinell, R. F., & Bjerrum, N. J. (2009). High temperature proton exchange membranes based on polybenzimidazoles for fuel cells. 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Ionic Conductive Polymers for Electrochemical Devices

Increasing levels of pollution and climate change are pushing the scientific community towards more sustainable solutions for the conversion and storage of energy. This book is dedicated to ionic conductive polymers, fundamental components of devices such as fuel cells (FCs), redox flow batteries (RFBs), and electrolyzers that can help to significantly decrease the amount of greenhouse gases emission. The book focuses on commercial polymers such as Nafion, a benchmark for proton-conducting membranes, acid doped polybenzimidazole (PBI), or blended membranes containing hyperbranched poly(arylene ether sulfone (PAES)/Linear poly(phenylene oxide) (PPO) as anion exchange membranes (AEMs). Promising and low-cost sulfonated aromatic polymers (SAP), or solid polymer blend electrolytes (SPBEs) based on natural chitosan (CS) and methylcellulose (MC). This book is also reports some strategies to enhance mechanical stability, such as cross-linking (XL), or several techniques, including classical casting methods or electrospinning (ES). I am confident that this book will serve to further stimulate advances in this research area, in both the sectors of membranes and catalysts, the first is essential for the long-term functioning of the system, and the second for a drastic reduction in costs, especially in fuel cells

Solids containing Si-O-P bonds: is the hydrolytic sol-gel route a suitable synthesis strategy?

Materials based on silicon-phosphorus mixed oxides have traditionally attracted interest in electronics, optics, catalysis, and related fields. The preparation of a solid containing stable Si–O–P linkages is a huge challenge due to their intrinsic instability to hydrolysis in a wet atmosphere. On the other hand, most technological applications of these materials, such as protonic conductive membranes in fuel cells and water-tolerant solid acid catalysts, are related to their interaction with water; consequently, suitable synthesis procedures that positively face this tradeoff are mandatory. Besides the traditional high-temperature techniques, sol-gel synthetic methods represent a viable, low-cost alternative, allowing for the preparation of high-purity materials with a homogeneous distribution of the components at the atomic scale. Si–O–P linkages are easily obtained by nonhydrolytic sol-gel routes, but only in inert and dry atmosphere. Conversely, hydrolytic routes offer opportunities to control the structure of the products in a wide range of processing conditions. The present review aims at providing an overall picture of the research on the sol-gel synthesis of phosphosilicate and related materials and theisr different applications, emphasizing how the interest in these systems is still lively, considering both conventional and emerging applications, such as flame retardance. The incorporation of Si–O–P nanostructures in polymer composites, coatings, and textiles is indeed a promising strategy to improve properties like thermal stability and fire resistance; however, their in-situ synthesis brings about additional difficulties related to the reactivity of the precursors. The perspectives linked with the development of Si–P-based materials are finally outlined