Cette étude est dédiée au développement de piles à combustible de type SOFC en configuration monochambre. L'originalité de ce type de pile SOFC est l'absence de séparation physique entre les compartiments anodique et cathodique. Un mélange d'hydrocarbure et d'air est injecté sur l'ensemble du dispositif comportant l'électrolyte et les deux électrodes de la pile SOFC. Le principe de fonctionnement de ce type de pile repose sur la différence d'activité catalytique entre les deux électrodes. L'anode doit être sélective pour l'oxydation des hydrocarbures et la cathode pour la réduction de l'oxygène. Cette configuration originale permet de s'affranchir des problèmes d'étanchéité des configurations conventionnelles deux atmosphères, ainsi que d'éviter les contraintes sur l'épaisseur de l'électrolyte suivant la disposition des électrodes (coplanaires ou de part et d'autre de l'électrolyte). Cette configuration conduit à des dispositifs simplifiés du point de vue technologique, et donc moins coûteux.<br />Dans cette étude, les électrodes ont été déposées en couches épaisses par la technologie de sérigraphie sur des pastilles support d'électrolyte. Au niveau matériaux, des électrolytes à base de cérine (en particulier GDC et SDC) ont été utilisés afin de diminuer la température de fonctionnement des piles de type SOFC (par rapport à celles avec un électrolyte YSZ). Des électrodes à propriétés catalytiques bien spécifiques vis à vis du mélange gazeux, ont été aussi étudiés : cermets Ni - GDC ou Ni - SDC pour l'anode, cathodes à base de LSM, BSCF ou SSC. Les poudres initiales ainsi que les couches sérigraphiées ont été caractérisées (analyse de phase, microstructure, stabilité chimique, conductivité électrique...) par diverses méthodes physico-chimiques. Différentes piles ont été élaborées et testées dans un réacteur monochambre sous des mélanges air-propane. L'influence des conditions gazeuses (débit, composition) ainsi que de la température de fonctionnement sur les performances des piles a été étudiée. Compte tenu de nos conditions de test, les performances se sont avérées relativement modestes (densité de puissance maximale de l'ordre de 12 mW.cm-2). Néanmoins, cette étude confirme la validité du concept des piles SOFC monochambres, et a aussi permis de développer un savoir-faire au niveau du laboratoire pour poursuivre les études sur cette thématique.

Made available in DSpace on 2016-03-15T19:36:49Z (GMT). No. of bitstreams: 1 Rafael Mezher Silva Pereira.pdf: 5290632 bytes, checksum: e2db559e31f1137c72cb9a649635434d (MD5) Previous issue date: 2015-01-30 / This paper studies the effects in a copper (Cu) alloy with the addition of Nickel (Ni), Silver (Ag) and Yttria (Y2O3), the metal-ceramic (cermet) alloy was manufactured by Powder Metallurgy (PM), this technique was chosen because it is advantageous when working with alloy elements with large difference in melting point, vapor pressure and density. It was used with the intention of creating a composite with good mechanical and electrical strength, capable to be measured by analyzing samples (including fractography) besides the usual experimental procedures of hardness and current tests. The results aim to explore some characteristics of this alloy as well as investigate and pursue such physical properties to meet current technology needs principally related as an option to anode of solid fuels or electrical contact in low temperatures. In general the study was satisfactory as it presents significant data especially in regard to the interaction of some physical characteristics on microscopic level of the components studied in this cermet that is still unknown and requires continued research. A fact that can be highlighted is the apparent lack of diffusion of Yttria particles that, as noted in the electronic mapping, were lodged between copper particles causing a not very homogeneous dispersion of the components in the alloy. This factor was most likely caused by low effectiveness compression and sintering of the samples, also impacting significantly on the hardness values and the conductivity values of about 29% IACS which measured in ambient temperature for metal alloys would be low, but for this metal-ceramic alloy is reasonable, as they have some inverse physical properties when exposed to cold temperatures resulting in lower resistivity values and higher critical temperatures making it suitable for low temperature electrical contacts. Y3 (Cu 90%/ Ni5%/ Ag3%/ Y2O32%) and Y6 (Cu 90%/ Ni7%/ Ag0%/ Y2O33%) samples with high concentration of Ni and low concentrations of Y2O3 had higher hardness values, and Y7 (Cu 95%/ Ni0%/ Ag0%/ Y2O35%) sample with high Cu concentration presented higher conductivity between all the samples. / Este trabalho estuda os efeitos da de Níquel (Ni), Prata (Ag) e Ítria (Y2O3) em uma liga de Cobre (Cu). Esta liga metal-cerâmica (cermeto) foi fabricada através da Metalurgia do Pó (MP), que foi escolhida pois é vantajosa quando se trabalha com ligas de elementos com grande diferença de ponto de fusão, pressão de vapor e densidade. Esta técnica foi utilizada objetivando criar um composto com resistência mecânica e elétrica e que pudesse ser mensurado e caracterizado através da análise de amostras por meio de procedimentos experimentais usuais de dureza e de corrente elétrica assim como fratografia. Os resultados mostram e exploram algumas características interessantes desta liga, e ao investigar tais propriedades físicas objetiva-se satisfazer as necessidades tecnológicas atuais principalmente como opções para uso como ânodo de combustível sólido ou como contato elétrico para baixas temperaturas. De modo geral o estudo foi satisfatório já que apresenta dados marcantes principalmente no que se diz respeito à interação de algumas características físicas a nível microscópico dos componentes estudados neste cermeto que ainda é pouco conhecido e requer continuidade de pesquisa. Um fato que pode ser ressaltado é a aparente não difusão das partículas de Ítria que, como observado nos mapeamentos eletrônicos, ficaram alojadas entre os aglutinados de cobre fazendo com que a dispersão dos componentes na liga não fosse homogênea. Tal fator muito provavelmente foi causado pela baixa eficácia da compactação e também da sinterização das amostras o que impactou consideravelmente nos valores de dureza que ficaram abaixo do esperado, assim como os valores de condutividade por volta de 29 %IACS que medidos a temperatura ambiente para uma liga exclusivamente metálica seria considerado baixo, mas no caso desta liga metal-cerâmica é bastante razoável. Já que possuem algumas propriedades físicas inversas quando submetidas a baixas temperaturas resultando em valores de resistividade mais baixos e temperaturas críticas mais elevadas ideais para contatos elétricos a baixa temperatura. As amostras Y3 (Cu 90%/ Ni5%/ Ag3%/ Y2O32%) e Y6 (Cu 90%/ Ni7%/ Ag0%/ Y2O33%) com alta concentração de Ni e baixa concentração de Y2O3 apresentaram maior dureza, e a amostra Y7 (Cu 95%/ Ni0%/ Ag0%/ Y2O35%) com alta concentração de Cu maior condutividade.

Stainless steel is a metal material widely used in many industries because of its high tensile strength, toughness, and corrosion resistance. Machining stainless steel is challenging due to its high work hardening tendency, low thermal conductivity, and ductility of the material resulting in built-up edge formation. Machining stainless steel at lower cutting speeds must be performed with coolant, which adds to the cost of the process and increases concerns for the environment and the operator's health and safety. Industries such as the aerospace and die-mold industries demand high-speed machining to realize productivity targets. Therefore, a cermet tool material was selected for the present study because of its high temperature resistance, high bending strength, and fracture toughness. The study focused on investigating wear mechanisms and developing a coating on a cermet tool for dry high-speed machining stainless steel to increase tool life. The wear mechanisms of tools were investigated at a fixed cutting interval in relation to the tool's composition and microstructure. Scanning Electron Microscope (SEM) was used to study the microstructure and identify elements on the tool. X-ray diffraction (XRD) was used to identify the phases and concentrations of key elements on the tool. The new advanced in-house coating was developed with Super Fine Cathode (SFC) technology on a Kobelco AIP-20 Physical Vapour Deposition (PVD) coater. The micromechanical properties of the commercial coating and in-house coatings were investigated with the help of nanoindentation and scratch tests. Atomic Force Microscopy (AFM) and SEM were used to investigate the coating microstructure and surface topography. An Alicona variable focus 3D microscope was used to investigate wear volume and wear behaviour. It was discovered that various secondary carbides used by manufacturers to manufacture cermet tools change the microstructure, which affects the machining performance of the cermet tool material. Microchipping at the depth of cut (DOC) causes catastrophic notch wear. It was found that the developed in-house coatings were able to delay the initial wear (microchipping), which improved the tool's life by 318%. This research contributes to meeting the manufacturing industry's challenging demand for dry-high speed machining with reduced manufacturing costs. / Thesis / Doctor of Philosophy (PhD) / Cutting is the process of removing unwanted material from the bulk material to obtain the desired shape. Each metal material has unique mechanical properties that lead to various machining challenges. The cutting process is done with the help of a cutting tool that wears out during the process, and a coating layer is often used to protect the tool. Stainless steel 304 is a widely used material that is difficult to machine. This study includes a systematic approach to understanding the wear mechanisms of tools and existing commercial coatings during the dry machining of stainless steel 304. An in-house coating was developed and deposited on the selected cutting tool to protect it, reduce tool wear and extend its working life. The research results will help reduce machining costs by reducing tool and coolant costs and meet the current industry demand for dry high-speed machining. It will also reduce environmental impact by reducing waste and hazardous chemicals and addressing occupational health and safety concerns.

Στο πρώτο μέρος της παρούσας διατριβής παρουσιάζεται ο σχεδιασμός, η κατασκευή και η λειτουργία μιας τριοδικής SOFC με state-of-the-art υλικά ηλεκτροδίων. Η τριοδική λειτουργία ενίσχυσε την απόδοση της κυψέλης έως και 7.7% κάτω από μη-ευνοϊκές συνθήκες λειτουργίας. Το δεύτερο μέρος αφορά τη μαθηματική μοντελοποίηση των SOFC. H μοντελοποίηση μόνιμης κατάστασης περιγράφει τη λειτουργία των κεραμομεταλλικών ανόδων μέσω ενός παράγοντα αποτελεσματικότητας, η, ο οποίος σχετίζεται με το αδιάστατο ρεύμα, J, και έναν αδιάστατο ρυθμό αντίδρασης, Φ2. Η μοντελοποίηση λαμβάνει υπ’όψη αποκλειστικά την υπερχείλιση ιόντων οξυγόνου από τον ηλεκτρολύτη και αφορά διάφορες γεωμετρίες των καταλυτικών σωματίων. Το μοντέλο επιβεβαιώνεται ικανοποιητικά από πειραματικά αποτελέσματα σε state-of-the-art κυψέλη SOFC. Για τη μοντελοποίηση της απενεργοποίησης των κεραμομεταλλικών ανόδων προτείνεται ότι η αύξηση του μεγέθους των καταλυτικών σωματίων Ni της ανόδου υπακούει σε μία συνάρτηση εκθετικής αύξησης της ακτίνας. Με τη χρήση θεμελιωδών ηλεκτροχημικών εξισώσεων σχετίζεται ο ρυθμός υποβάθμισης με τη μεταβολή του μήκους ορίου τριών φάσεων, που υπολογίζεται από την συνάρτηση εκθετικής αύξησης της ακτίνας, και με δομικές και λειτουργικές παραμέτρους της ανόδου. Το μοντέλο επιβεβαιώνεται από πειραματικά δεδομένα συστοιχιών SOFC. Τέλος, μελετώνται οι ιδιότητες των κεραμομεταλλικών ανόδων με τη μέθοδο της Θερμοπρογραμματιζόμενης εκρόφησης. Με τη μέθοδο της αέριας ρόφησης αναγνωρίστηκαν τρία κύρια είδη κορυφών τα οποία είναι σε συμφωνία με κορυφές που έχουν παρατηρηθεί σε αντίστοιχα συστήματα. Εκτιμήθηκαν οι ενέργειες ενεργοποίησης της εκρόφησης των κορυφών. Με τη μέθοδο της ηλεκτροχημικής ρόφησης επιβεβαιώθηκε η ύπαρξη των κορυφών και παρατηρήθηκε μετατόπιση της κύριας κορυφής σε υψηλότερη θερμοκρασία εκρόφησης υποδηλώνοντας ισχυρότερη σύνδεση με τον καταλύτη, σε συμφωνία με τη βιβλιογραφία. / In the first part of the present dissertation the design, construction and operation of a triode SOFC with state-of-the-art electrode materials is presented. The triode operation led to an increased performance of the fuel cell up to 7.7% under unfavorable operating conditions. The second part of the dissertation regards the mathematical modeling of SOFC cermet anodes. Under steady state conditions the operation of the cermet anode is described via the use of an effectiveness factor, η, that is related to the dimensionless current of the anode, J, and a dimensionless reaction rate, Φ2. The modeling accounts explicitly for the migration of the oxygen spillover species from the electrolyte and examines various geometries of the catalytic particles. The model is in good agreement with experimental data obtained from state-of-the-art SOFC cells. For the anode degradation modeling it is proposed that the radius of the Ni particles of the follows an exponential growth function, to describe the sintering induced particle growth. Using fundamental electrochemical equations the degradation is linked to the three phase boundary length, that can be estimated from the exponentially growing radius, and operational and structural data of the anode. The model is validated using SOFC stack experimental data. The third part involves the study of SOFC cermet anodes with the use of Temperature Programmed Desorption. Using gaseous adsorption we identified three peaks that are in agreement with peaks observed in similar systems. The activation energies of the desorption peaks were calculated. Using electrochemical adsorption we verified the origin of the peaks. The shift of the main peak towards higher desorption temperature implies stronger bonding of the relevant species with the catalyst, in agreement with literature data.

Diplomová práce se zabývá analýzou technologie vysoceproduktivního vystružování. V rámci práce byly provedeny testy vystružování za různých technologických podmínek (vc=40, 60, 80, 100 m/min; f=0.2, 0.4, 0.6, 0.8 mm) na materiálu austenitické oceli DIN 1.4404 při použití vystružovací hlavicí MT3. Jednotlivé operace vystružování byly porovnány z hlediska parametrů jako tlačná síla, krouticí moment, výsledná drsnost obrobeného povrchu a dále z hlediska tvaru třísky. Následně byly vypočítány průměrné hodnoty a směrodatná odchylka naměřených parametrů. Dále bylo provedeno porovnání pomocí diagramů. Výsledky ukazují lepší kvalitu, nižší drsnost povrchu (Ra 0,37 µm) a méně zdeformovanou třísku při pomalejších řezných rychlostech (40 m/min) a menším posuvu na otáčku (0,2 mm). Výsledky také ukazují nárůst tlačné síly a krouticího momentu za uvedených technologických podmínek. Při zvyšující se řezné rychlosti vystružování tyto silové účinky klesají.