Limiter le vieillissement des accumulateurs lithium-ion est un challenge pour optimiser leur utilisation notamment dans le domaine spatial. La qualité de la couche de passivation (SEI), formée à la surface de l’électrode négative de graphite lors des premiers cycles de vie de la batterie, est déterminante pour ses performances futures. Celle-ci est composée de polymères et de divers sels de lithium dont la dissolution, la précipitation et la migration affectent les performances. Cette étude vise à comprendre l’impact de ces composés sur la cyclabilité et de proposer des solutions à l’effet néfaste de ces sels sur le bon fonctionnement et le vieillissement de l’accumulateur Li-ion. La première partie de ce travail aborde l’impact de divers sels de lithium de la SEI (LiF, Li2CO3, LiOH, LiOCH3, LiOC2H5) sur le comportement en cyclage des accumulateurs. Par la suite, nous avons proposé des solutions pour améliorer le comportement qu’engendre la présence de ces sels sur les performances à travers deux approches. La première concerne l’utilisation de co-solvants complexants de la famille des glymes. La seconde approche consiste à modifier les propriétés interfaciales électrodes/électrolyte par l’ajout d’additifs tensioactifs à l’électrolyte. Les résultats montrent dans les deux cas des améliorations notables de la cyclabilité des dispositifs en demi-pile et en cellule complète. / Limiting the lithium-ion batteries ageing is a challenge to overcome in the field of spatial applications. The quality of the solid electrolyte interfaces (SEI), created at the electrode surface during the first cycles of the battery, is decisive for its future performances. The SEI is composed of polymers and several lithium salts which are able to dissolve, precipitate and migrate in the electrolyte and hence modify the battery performances. This study aims to understand the impact of the dissolution of these compounds on the cell cycling ability and to propose solutions to avoid the harmful effects of these salts on the battery ageing. The first part of this study is devoted to the study of the effect of dissolved SEI lithium salts (LiF, LiOH, Li2O, Li2CO3 , LiOCH3, LiOC2H5) on the cycling ability of half and full cells.In order to improve the battery performances in spite of the presence of these SEI salts in the electrolyte, two solutions have been examined. The first one is to add a co-solvent belonging to the glyme family which is able to form complexes with lithium ions and the second to use a surfactant additive which will modify the interfacial electrode/electrolyte properties. Results show that in both cases an improvement in half-cell or full-cell cycling ability was achieved.

Neuere Erzeugnisse zeichnen sich häufig durch eine Werkstoffvielfalt aus. Teilweise sind die Werkstoffe thermisch empfindlich. Aus allen diesen Gründen wird das weitgehend werkstoffunspezifische und wärmearme Verfahren Kleben für das Fügen von Bauteilstrukturen immer wichtiger. Es ist seit langem bekannt, dass die Festigkeit und vor allem die Alterungsbeständigkeit der Klebverbindungen neben der Art des gewählten Klebstoffes in ganz wesentlichem Umfang von den physikalischen, chemischen und morphologischen Eigenschaften der Fügeteiloberflächen abhängig ist. Die Eigenschaft der Klebverbindung wird nicht vorrangig durch die Haftung an der Fügeoberfläche, sondern durch den grenzflächennahen Polymerbereich, der so genannten Interphase oder Grenzschicht bestimmt. Ziel dieser Forschung ist daher die Untersuchung von Grenzflächenphänomenen des Verbundes Aluminium/ Epoxid-Klebstoff im µm-Bereich in Abhängigkeit von unterschiedlich vorbehandelten Aluminiumoberflächen unter Einschluss von Haftvermittlersauftrag durch thermoanalytische, spektroskopische, mikroskopische und elektrochemische Methoden, sowie die Korrelation der Ergebnisse mit den Festigkeiten und Langzeitbeständigkeiten der Klebverbindungen. Die in der Arbeit gewonnenen Erkenntnisse und erzielten Ergebnisse können in der Fügetechnik betriebswirtschaftlich sehr vorteilhaft zur Behandlung von Fügeteilen aus Aluminiumlegierungen angewendet werden.

Carbon nanotubes are known as one of the strongest materials in nature and since their discovery; they have triggered the scientific interest for fabricating multi-functional polymer composites. However, a well-known problem associated to the incorporation of nanoparticulate materials in polymer matrices is their tendency to agglomerate in order to reduce their surface energy, and the extreme increase of the polymer viscosities (i.e melts, solutions, etc), which makes it very difficult to process them. Polymers can be efficiently reinforced by fibers for applications where high strength and stiffness are required. Micro-scale short fiber reinforced polymer composites have been an alternative way to obtain fiber reinforced composites since the long fiber incorporation is a painful job and not always feasible and easy to produce composites in big scale. Therefore, use of long glass fibers as the support for depositing CNTs as well as CNTs+other kind of nanoparticles was made, and the resulting interfaces were investigated in detail by single fiber model composites. This approach can bring the CNT functionality, fiber strength and toughness to the final composite, and simultaneously alleviate the manufacturing process from increase of the polymer high viscosities. Finally, very logically the question of whether to improve or destroy the interface integrity comes before implementing the hybrid hierarchical reinforcements in bigger scales, and an output out of this work will be given. Furthermore, several information and functionalities arising from the CNTs at the interphase region will be elucidated like cure monitoring of the epoxy resin matrix, UV-sensing ability, and thermoelectric energy harvesting, giving rise to multi-functional structural composites. CNT-modified natural fibers also have been utillised to fabricate short fiber reinforced composites, and have shown a promising reinforcement effect due to the CNT nanostructured interfaces. The ‘interface’ in fiber reinforced polymer composites (FRPCs) is known as a very crucial parameter that has to be considered in the design of a composite with desired properties. Interfaces are often considered as surfaces however, they are in fact zones or areas with compositional, structural, and property gradients, typically varying from that of the fiber and the matrix material. Characterization of the mechanical properties of interfaces is necessary for understanding the mechanical behavior of scaled-up composites. In fact, the mechanical characteristics of a fiber/resin composite depend mainly on i) the mechanical properties of the component materials, ii) the surface of the fiber, and iii) the nature of the fiber/resin bonding as well as the mode of stress transfer at the interface. Among the many factors that govern the characteristics of composites involving a glass, carbon, natural or ceramic fiber, and a macromolecular matrix, the adhesion between fiber and matrix plays a predominant role. In specific, the stress transfer at the interface requires an efficient coupling between fiber and matrix. Therefore, it is important to optimize the interfacial bonding since a direct linkage between fiber and matrix gives rise to a rigid, low impact resistance composite material.

Diss. (sammanfattning) Umeå : Umeå universitet, 2008. / Härtill 4 uppsatser.

Ce travail de thèse est consacré à la caractérisation des propriétés mécaniques de l’interphase pâte de ciment-granulat au cours de l’hydratation et au cours de la dégradation chimique par lixiviation. La microstructure de l'interphase entre la pâte de ciment et les granulats est caractérisée par une porosité supérieure à celle de la pâte de ciment. Cette zone constitue un point de fragilité dans le béton et ses propriétés affectent fortement le comportement mécanique du béton à l’échelle macroscopique et à l’échelle de la structure. Dans ce travail, la résistance de l’interphase pâte de ciment-granulat est analysée expérimentalement à l'échelle locale. Des essais expérimentaux sont réalisés sur des composites constitués de granulats liés par une pâte de ciment portland préparée avec un rapport Eau/Ciment de 0,5. Des dispositifs expérimentaux dédiés ont été conçus et réalisés de manière à être adaptés à la taille et à la forme des échantillons. La forme des échantillons utilisés et les outils expérimentaux développés permettent de solliciter directement l’interphase. A différents stades de l'hydratation, des échantillons de pâte de ciment seule et des composites sont soumis à des essais de compression, de traction et de cisaillement direct. L’étude des propriétés mécaniques de l’interphase pâte de ciment-granulat révèle une faiblesse de cette zone en termes de propriétés mécaniques..Le protocole expérimental mis au point a permis d’étudier les effets du mécanisme de lixiviation du calcium au niveau de l’interphase sur les propriétés mécaniques du béton à l’échelle locale. Compte tenu du temps caractéristique long du phénomène de lixiviation, la mise en situation expérimentale au laboratoire est accélérée en remplaçant l’eau par une solution de nitrate d'ammonium. Afin de quantifier le développement et la cinétique de dégradation au niveau de la liaison cimentée, les fronts de lixiviation du béton sont caractérisés à différents degrés de dégradation en utilisant la phénolphtaléine comme traceur. Des essais mécaniques locaux (compression, traction et cisaillement) sont réalisés sur les composites et sur la pâte de ciment à différents temps de dégradation. L’étude de l’effet de la lixiviation à l’échelle locale montre le rôle important de l’interphase pâte de ciment-granulat lors du processus de dégradation chimique sur les propriétés mécaniques du composite. / In this work, we presents an experimental study to characterize the mechanical properties at the local scale of the cement paste-aggregate interface during hydration and during chemical degradation by leaching.It is generally accepted that the microstructure of the interface between the aggregates and the cement paste is characterized by a higher porosity than that of cement paste. This makes this zone a weak point in the concrete. The particular properties of this zone strongly influence the mechanical behavior of concrete. In this work, the mechanical properties of the cement paste-aggregate composite, are experimentally studied. The experimental tests are performed on composites at classical aggregate scale (one centimeter of section). These composite are composed by and Portland cement paste and aggregate. The cement paste is prepared with a water/cement ratio of 0.5. The shape of the prepared composites makes them convenient for direct tensile and shear tests. At different stages of hydration, we performed direct tensile and shear tests on the composites by means of specific devices. The same tests were carried out on the cement paste in order to compare with composites results. The shape of the prepared composites makes them convenient to characterize the cement paste-aggregate interface. At different stages of hydration, the composites are subjected to compression tests, direct tensile tests or shear tests. The study of the mechanical properties of the cement-aggregates interface revealed that the cement paste-aggregate interface is the weakest zone in the composite.An experimental protocol was developed to study the effects of calcium leaching mechanism at the cement paste-aggregate interface on the mechanical properties of the concrete. As the process of leaching with the deionised water occurs very slowly, the experimental study in the laboratory is accelerated by replacing the water by ammonium nitrate solution. To quantify the development and kinetics of degradation at the cemented bond, the concrete leaching fronts are characterized at different levels of degradation by using phenolphthalein. Local mechanical tests (compression, tensile and shear) are performed on composite and cement paste at different stages of degradation. The experimental results show that there is a leaching effect on the alteration of the mechanical properties at the cement paste-aggregate interface.

Orientadores: Amauri Garcia, Jose Eduardo Spinelli / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-12T23:27:26Z (GMT). No. of bitstreams: 1 Silva_MariaAdrinaPaixaodeSouzada_M.pdf: 3527327 bytes, checksum: 88f3012a000dcdb2956852ed7fa40402 (MD5) Previous issue date: 2008 / Resumo: Ligas de alumínio dispersas com bismuto apresentam aplicações promissoras em componentes automotivos resistentes ao desgaste. Essas dispersões de elementos de baixa temperatura de fusão diminuem a dureza e escoam facilmente em condições de deslizamento, resultando em um comportamento tribológico favorável. Muitos estudos têm sido realizados a fim de melhor compreender as distintas morfologias obtidas pela reação monotética. Algumas pesquisas assumem que a evolução do espaçamento interfásico na liga monotética Al-Bi obedece à clássica relação utilizada para eutéticos: ?2v = C, onde v é a velocidade de solidificação e C é uma constante. Não há nenhum consenso a respeito dos valores de C encontrados. Além disso, tais estudos utilizaram fornos de aquecimento à resistência do tipo Bridgman para produzir a solidificação direcional de ligas monotéticas. Existe uma falta de estudos consistentes no desenvolvimento microestrutural de ligas monotéticas durante condições de fluxo de calor transitório, que são de importância primordial, uma vez que esse tipo de fluxo de calor engloba a maioria dos processos industriais de solidificação. No presente estudo, foram feitos experimentos de solidificação unidirecional em regime não-estacionário com as ligas hipomonotética Al-2,0%Bi e monotética Al-3,2%Bi. Os parâmetros térmicos como velocidades de crescimento, taxas de resfriamento e gradientes térmicos foram determinados experimentalmente por curvas de resfriamento adquiridas ao longo do comprimento do lingote. Os crescimentos celular e monotético foram caracterizados por técnicas metalográficas, e os espaçamentos celulares e interfásicos correlacionados com os parâmetros térmicos de solidificação. Verificou-se que a lei de crescimento ?2v = C pode ser expressa por um valor de C de 1,70 x10-12, que é em torno de duas ordens de magnitude maior do que aqueles reportados para o regime estacionário. Embora o fluxo convectivo induzido não tenha sido suficiente para mudanças consideráveis na magnitude dos espaçamentos interfásicos, as partículas ricas em bismuto foram afetadas pela direção do crescimento, diminuindo o diâmetro em condições de solidificação vertical descendente, quando comparadas com aquelas obtidas no modo vertical ascendente / Abstract: Aluminium alloys dispersed with bismuth show promising applications in wear-resistant automotive components. Such dispersions of low melting temperature elements decrease hardness and flow easily under sliding conditions, resulting in favorable tribological behavior. Much research has been devoted in order to better comprehend the distinct morphologies obtained by monotectic reaction. Some researches assume that the phase spacing evolution in the monotectic Al-Bi alloy follows the classical relationship used for eutectics: ?2v = C, where v is the solidification velocity and C a constant value. There is no consensus concerning the found C values. Other than, such studies have used Bridgman-type resistance heated furnaces to produce the directionally solidified monotectic samples. There is a lack of consistent studies on the microstructural development of monotectic Al-Bi alloy during transient heat flow conditions, which are of prime importance since this class of heat flow encompasses the majority of solidification industrial processes. In the present study, directional unsteady-state solidification experiments were carried out with hypomonotectic Al-2.0wt%Bi and monotectic Al-3.2wt%Bi alloys. The thermal parameters such as growth rates, cooling rates and thermal gradients were experimentally determined by cooling curves recorded along the casting length. The cellular and monotectic growths were characterized by metallography, being both the cell and the interphase spacing correlated with the thermal parameters. It is shown that the ?2v = C growth law can be expressed by a C value of 1,7x10-12, which is about two orders of magnitude higher than those reported for the steady-state regime. Although the induced convective flow was not enough to considerably change the interphase spacing's magnitude, the Bi-rich particle diameters have been affected by the direction of growth, decreasing in conditions of downward vertical solidification when compared with those grown vertically upwards / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Abstract The main object of this thesis was to research injection mouldable 0–3 type ceramic polymer composites and their dielectric and magnetic properties in the GHz frequency region. The work has been divided into three sections. In the first section, two–phase ceramic polymer composites containing dielectric and magnetic fillers have been investigated and their characteristics analysed by reference to pre–existing mixing rules. The exploitation of these composites in miniaturizing devices, such as antennae, is presented and discussed. The second part describes three phase composites containing different nanosize additives (silver, silicon and alumina fibres) towards improving their dielectric properties. In the third part, some periodical and multilayer structures for ceramic polymer composite layers are proposed. In the case of two–phase ceramic polymer composites, with 37 vol.% of dielectric filler (Barium Strontium Titanate, BST) embedded into a thermoplastic polymer (ER140) matrix, the highest measured relative permittivity was 15 with a dielectric loss value of 0.008 at 1 GHz. With 43 vol.% of magnetic filler (hexaferrite, CO2Z) in ER182 matrix, the highest achieved relative permeability was 1.8 with a magnetic loss value of 0.077 at 1 GHz. Composites with Co2Z filler provide a 77% size reduction, and could thus be used advantageously in antennae. It was found that a 2–6 vol.% nanoaddition in BST–ER140 composites enhanced the relative permittivity drastically with only a minor effect on the dielectric losses. In particular, with only 2 vol.% addition of nanosize silver particles into the BST–ER140 composite, a 52% increase in the relative permittivity was obtained, with no significant change in the dielectric losses (tan δε = 0.004). Vertically and horizontally periodical dielectric composite structures comprising layers of different dielectric properties have been fabricated as well as multilayered structures containing dielectric and magnetic layers. The measurement results indicate that such multimaterial multilayer structures are good candidates for components with reduced dielectric and magnetic losses. / Tiivistelmä Väitöstyön tavoitteena oli tutkia ruiskuvalettavien 0–3 –liitännäisten keraami-polymeerikomposiittien ominaisuuksia erityisesti niiden GHz-taajuusalueen dielektristen ja magneettisten ominaisuuksien kannalta. Työ on jaettu kolmeen osaan. Ensimmäisessä osassa on tutkittu kaksikomponenttisia keraami-polymeerikomposiitteja, joissa täytemateriaali on joko dielektristä tai magneettista materiaalia. Komposiittien ominaisuuksia on analysoitu jo olemassa olevien seosmallinnuskaavojen avulla. Komposiittien hyödyntämistä erilaisten sovellusten, kuten antennien, minityrisoinnissa on myös käsitelty. Toinen osa käsittelee kolmikomponenttisia komposiitteja, joissa lisäaineena on käytetty pieniä määriä nanomateriaaleja (hopea- ja piipartikkelit sekä alumiinioksidikuitu) tarkoituksena parantaa komposiitin dielektrisiä. Kolmannessa osassa on tutkittu periodisia ja monikerroksisia keraami- polymeerikomposiittirakenteita rakenteita. Kaksikomponenttisten keraami-polymeerikomposiittien tapauksessa suurin permittiivisyyden arvo 15 dielektristen häviöiden ollessa 0.008 (mittaustaajuus 1 GHz) saatiin komposiitille, jossa dielektristä täytemateriaalia (Barium Strontium Titanaatti, BST) oli 37 tilavuus-% termoplastisessa polymeerimatriisissa (ER140). Korkein saavutettu permeabiliteetin arvo 1.8 magneettisten häviöiden ollessa 0.077 (mittaustaajuus 1 GHz) saatiin komposiitille, jossa magneettista täyteainetta (hexaferriitti, Co2Z) oli 43 tilavuus-% ER182 -matriisissa. Tämä täyteaine mahdollistaa nykyistä jopa 77 % pienempien antennielementtien kehittämisen. Tukimuksessa todettiin 2–6 tilavuus-% nanomateriaalin lisäyksen BST-ER140 -komposiitteihin kasvattavan permittiivisyyttä merkittävästi juurikaan vaikuttamatta dielektrisiin häviöihin. Erityisesti 2 tilavuus-% hopeananopartikkeleiden lisäys BST-ER140 -komposiitteihin kasvatti permittiivisyyttä 52 % dielektristen häviöiden (tan δε =  0.004) kasvamatta. Työssä on myös tutkittu periodisesti (vertikaali ja horisontaali) koostettuja dielektrisiä komposiittirakenteita, jossa eri kerroksissa on erilaiset dielektriset ominaisuudet sekä monikerrosrakenteita, joissa vuorottelevat dielektriset ja magneettiset kerrokset. Mittaukset osoittivat, että monimateriaaliset monikerrosrakenteet ovat hyviä kandidaatteja komponentteihin, jotka vaativat pieniä dielektrisiä ja magneettisiä häviöitä.

Surfaces of carbon fibre roving were modified by means of a low temperature plasma treatment to improve their bonding with mineral fines; the latter serving as an inorganic fibre coating for the improved mechanical performance of carbon reinforcement in concrete matrices. Variation of the plasma conditions, such as gas composition and treatment time, was accomplished to establish polar groups on the carbon fibres prior to contact with the suspension of mineral particles in water. Subsequently, the rovings were implemented in a fine concrete matrix and their pull-out performance was assessed. Every plasma treatment resulted in increased pull-out forces in comparison to the reference samples without plasma treatment, indicating a better bonding between the mineral coating material and the carbon fibres. Significant differences were found, depending on gas composition and treatment time. Microscopic investigations showed that the samples with the highest pull-out force exhibited carbon fibre surfaces with the largest areas of hydration products grown on them. Additionally, the coating material ingresses into the multifilament roving in these specimens, leading to better force transfer between individual carbon filaments and between the entire roving and surrounding matrix, thus explaining the superior mechanical performance of the specimens containing appropriately plasma-treated carbon roving.

Cieľom diplomovej práce je príprava polymerných kompozitov vyztužených sklenenými vláknami s riadenou medzifázou za použitia metódy plazmochemickej depozície z plynnej fáze a monomeru tetravinylsilanu. Teoretická časť je zameraná na literárnu rešerš o plazme, plazmovej polymerácií, tenkých vrstvách a kompozitoch. Experimentálna časť popisuje použité materiály a aparaturu použitú na povrchovú modifikáciu sklenených vlákien a prípravu vláknom vyztužených kompozitov. Povrchová úprava sklenených vlákien prebiehala za rôznych depozičných podmienok. Chemické a mechanické analýzy vytvorenej medzivrstvy prebiehali za použitia FTIR spektrometrie a vrypového testu. Vliv povrchovej úpravy bol zistený pomocou získanej interlaminárnej šmykovej sily použítím testu krátkych trámečkov.

Diploma thesis deals with the research of oxide interphase of ceramic composite in dependence on the amount of precursor used in sol – gel method for deposition of titanium dioxide thin layer on corundum.