O presente trabalho trata da preparação e da caracterização de sistemas contendo tetrassulfoftalocianinas de Co(II) (CoPcTs) e Fe(III) (FePcTs) intercaladas ou somente adsorvidas externamente em matrizes de hidróxidos duplos lamelares (HDLs). Foram sintetizados materiais com composições variadas e empregando-se diferentes métodos de síntese visando, principalmente, o isolamento de materiais com microporosidade intracristalina e/ou com um baixo grau de agregação da ftalocianina. Técnicas de caracterização textural (difração de raios-X e medidas de área superficial) e espectroscópicas (vibracional na região do infravermelho, eletrônica no UV/visível, ressonância paramagnética eletrônica e absorção de raios-X), além das análises elementar (C, H, N e metais) e termogravimétrica foram utilizadas para a caracterização dos sólidos sintetizados. Avaliaram-se os materiais como catalisadores na reação de oxidação do 2,6-di-terc-butilfenol e do catecol, utilizando O2ou H2O2 como oxidantes. Nos materiais isolados contendo a CoPcTs intercalada em HDLs com composição MgxAl (x = 2, 3 e 4) e ZnxAl (x = 4 e 5), a ftalocianina está orientada perpendicularmente às lamelas do HDL, independentemente do método de síntese e da composição dos HDLs utilizados. Adicionalmente, constatou-se que a CoPcTs intercalada está altamente agregada e que os materiais não possuem microporosidade. Porém, a diminuição da densidade de carga do HDL provoca uma pequena diminuição na agregação da CoPcTs. Sob determinada condição sintética, a CoPcTs intercalada nos HDLs ZnxAl sofre o processo de enxertia através dos grupos sulfônicos. Quando testados como catalisadores na oxidação do 2,6-di-terc-butilfenol, os materiais contendo a CoPcTs intercalada e enxertada apresentaram reatividade inexpressiva, que pode ser devida ao acesso restrito do substrato ao sítio ativo na região interlamelar. Estudos de adsorção da FePcTs em HDLs MgxAl na forma carbonato, investigados por espectroscopia eletrônica UV/Visível in situ, mostraram uma elevada tendência de agregação da ftalocianina na superfície dos HDLs. Os espectros eletrônicos indicaram também que diferentes espécies derivadas da FePcTs são formadas durante o processo de adsorção nos HDLs e que a densidade de carga influencia o tipo de espécie adsorvida: há predominância de um dímero do tipo µ-oxo nos HDLs Mg2Al e Mg3Al e do dímero (FePcTs)2 no HDL Mg4Al. Os espectros de absorção de raios-X (XANES) da FePcTs adsorvida nos HDLs MgxAl mostraram que as espécies adsorvidas apresentam geometria piramidal de base quadrada (C4v) e/ou octaédrica (Oh), corroborando com os dados de espectroscopia no UV/Visível. Já os espectros de ressonância paramagnética eletrônica mostraram que a ftalocianina de Fe(III) quando adsorvida nos HDLs gera uma mistura de espécies com configuração de baixo spin e alto spin e, também, elevada distorção rômbica. A FePcTs adsorvida nos HDLs MgxAl apresentou estabilidade e reatividade catalítica superior quando comparada com a ftalocianina livre na oxidação dos fenóis. A ftalocianina adsorvida na superfície externa do HDL deve favorecer o acesso do substrato ao sítio ativo. Uma correlação entre os estudos de adsorção e os resultados dos testes catalíticos mostrou que a espécie dimérica do tipo µ-oxo pode ser a espécie mais ativa na oxidação dos fenóis. Nestes sistemas, as camadas positivas do HDL devem provocar um enfraquecimento da ligação O-H do fenol, facilitando a sua desprotonação (uma das etapas do mecanismo de oxidação). Este último efeito pareceu atuante, pois foram observadas reatividades crescentes dos catalisadores à medida que se aumentava a densidade de carga do HDL. Estes resultados indicaram que existe um efeito cooperativo nos HDLs MgxAl contendo a FePcTs adsorvida, mostrando que o HDL não atua como um suporte inerte nos processos estudados. / The present work describes the preparation and characterization of materials containing Co(II) and Fe(III) tetrasulfonated phthalocyanines (CoPcTs and FePcTs, respectively) intercalated or adsorbed on layered double hydroxides (LDHs). Different compositions and synthetic methods were used to isolate materials with microporosity and/or the phthalocyanine in a low aggregation degree. X-ray diffraction analysis, surface area measurements, spectroscopic techniques (infrared, UV/visible and X-ray absorption), elemental analysis and thermogravimetry were used to characterize the solids. The materials were tested as catalysts in the 2,6-di-terc-butilfenol and catechol oxidation, using O2 or H2O2 as oxidants. In the materials prepared by intercalation of the CoPcTs in MgxAl (x = 2, 3 and 4) and ZnxAl (x = 4 and 5) LDHs, the phthalocyanine is perpendicularly orientated related to the LDH layers, regardless of synthetic method or LDH composition used. In addition, it was observed that the intercalated phthalocyanine is aggregated and the solids do not have microporous. However, the aggregation degree of the phthalocyanine is slightly lower when the LDH charge density decreases. Under a particular synthetic conditions the CoPcTs intercalated in the LDH ZnxAl is grafted through the sulfonic groups. Catalytic tests uisng this material in the 2,6-di-terc-butilfenol oxidation showed a neglectful reactivity, which confirms the aggregation of the intercalated CoPcTs, thus avoiding that the substrate accesses the reactive center. In an adsorption study carried by monitoring in situ the FePcTs UV/Vis electronic spectra during its addition to LDH suspensions, a strong tendency of aggregation was observed for the FePcTs. In addition, different FePcTs species are formed during the adsorption process on the LDHs, which is influenced by the LDH charge density: the µ-oxo complex is the main species adsorbed on the Mg2Al and Mg3Al LDHs, whereas for Mg4Al the non oxo-bridged dimeric complex prevailed. X-ray absorption spectra (XANES) of the adsorbed FePcTs on the MgxAl LDHs showed that the species present a square-pyramidal (C4v) and/or an octahedral (Oh) symmetry, in agreement with the UV/visible spectroscopic data. EPR spectra of these samples showed that the FePcTs adsorbed on the LDHs leads to a mixture of Fe(III) high and low spin species along with a strong rhombic distortion. The FePcTs adsorbed on the MgxAl LDHs showed an enhanced catalytic activity and longevity in the phenols oxidation compared to the homogeneous counterpart. The phthalocyanine on the LDH external surfaces allows the access of the substrate to the reactive metal center. A correlation between the adsorption study and the catalytic tests pointed that the FePcTs µ-oxo complex may be the active species in the oxidation of phenols. Furthermore, the positive charge of LDH layers may weaken the O-H bonding in the phenol molecules making them more easily ionized (one step of the phenol oxidation mechanism). This feature seems to be effective because higher activities of the catalysts were observed along with increasing charge density of the LDHs. These results indicated that a cooperative effect takes place in the materials containing the FePcTs adsorbed on the MgxAl LDHs, showing that LDH do not act as an inert support in the studied catalytic reactions.

La compréhension et l’amélioration de l’environnement vibratoire des charges utiles demande la mise au point de démarches prédictives maîtrisées qui permettent de comprendre les phénomènes de transmission des ondes de chocs d’origine pyrotechnique dans le lanceur Ariane5. Plus particulièrement, la maîtrise du comportement transitoire des coques sandwichs en nid d’abeilles, principaux constituants de l’Adaptateur de Charges Utiles – structure porteuse des satellites, est nécessaire pour prédire les vibrations au pied des équipements électroniques des satellites et des lanceurs. Cette problématique présente un caractère multi-échelle tant d’un point de vue temporel (charge mobile supersonique, temps d’analyse) que spatial (dimensions des structures du lanceur, taille des cellules en nid d’abeilles, longueurs d’ondes liées aux hautes fréquences). Celui-ci a été traité dans cette thèse en s’appuyant d’une part, sur une qualification à la fois analytique et numérique des modèles classiques homogénéisés des plaques sandwichs en nid d’abeilles pour la gamme de fréquence mise en jeu et d’autre part, sur une application des stratégies de remaillage adaptatif pour la propagation des ondes développées dans le cadre de la méthode de Galerkin espace-temps discontinue en temps. Deux catégories de modèles de plaques épaisses ont été ainsi construites dans le but d’enrichir la cinématique classique de plaques épaisses de Mindlin-Reissner qui s’est avérée être insuffisante pour correctement représenter le comportement dynamique hors-plan des plaques sandwich en nid d’abeilles. Ainsi ont été analysés les modèles dits monocouches basés sur un enrichissement de la cinématique par ajout de degrés de liberté dans l’épaisseur, et les modèles multicouches composés d’une superposition de trois plaques avec une homogénéisation séparée des matériaux. Il a été montré que ces deux sortes de modèles améliorent la description des phénomènes de hautes fréquences, notamment ceux de flexion et de cisaillement transverse qui sont plus délicats à retranscrire. Toutes les études numériques ont été effectuées avec un code éléments finis qui emploie des solveurs adaptatifs dynamiques basés sur la méthode de Galerkin espace-temps discontinue en temps. Cette méthode d’intégration en temps introduit un amortissement numérique dépendant du pas de temps et qui peut interférer avec un amortissement physique susceptible d’être introduit dans un modèle numérique et conduire au final à un amortissement total différent de celui qui est attendu. Cette interaction a été analysée et mise en évidence dans ce travail à travers l’introduction de l’amortissement de Rayleigh dans les modèles de propagation de chocs. Les outils et les modèles de propagation ainsi développés ont été validés sur plusieurs structures académiques et industrielles. Des comparaisons avec des données expérimentales sur des structures industrielles de grande taille, plus particulièrement sur un Adaptateur de Charges Utiles d’Ariane5, sont effectuées et soulignent la cohérence de notre approche ainsi que la fiabilité et l’efficacité des modèles de propagation proposés. / Reliable and efficient numerical models for the pyrotechnic shock wave propagation in structures of the Ariane5 launcher are necessary for a good understanding and a predictive analysis of the payload vibration environment. More precisely, the correct modeling of the dynamic behaviour of the honeycomb sandwich shells, the main material composing the payload adaptor, is essential to control the vibration environment of the payload and the embarked electronic equipments and so to prevent them from damages caused by the shock wave propagation. The topic is obviously a multi-scale problem from both temporal and spatial points of view : short time intervals imposed by supersonic moving loads vs. large total time interval that the slowest waves need to travel throughout the adaptor ; very short wavelengths of high frequency waves, and very small size of the honeycomb cells vs. large structure dimensions. To take into account all involved space-time scales in a reliable and efficient way, the herein study is based both on the analytical and numerical qualification of the classical homogenized models of honeycomb sandwich shells for the frequency range introduced by the pyrotechnic shock wave, and on a dynamic solver based on the well-known space-time discontinuous Galerkin method, allowing the use of adaptive remeshes for the wave propagation. The classical Mindlin-Reissner’s kinematics of thick plates being inefficient to correctly represent the dynamic out-of-plane behaviour of the honeycomb sandwich plates, two kinds of its enrichment are considered : One-layered models based on an enrichment of the kinematics by adding degrees of freedom in the thickness, and multi-layered models composed of a superposition of three plates with separated material homogenisations. It has been shown theoretically and numerically that, both types of enrichment allow more precise descriptions of flexure and transverse shear modes in the high frequency range. However, the multi-layered models give much more promising results, as the important role played by the honeycomb core for the transverse shear behaviour of the whole sandwich is not “smeared” in a one-layered homogenized model. All the numerical studies were conducted with a finite element code which uses a dynamic solverbased on the time discontinuous space-time Galerkin method. The built-in numerical damping of this solver can interfere with a physical damping potentially introduced by the numerical model and results in a global damping totally unexpected. This interaction has been analysed and underlined in this work thanks to the introduction of the Rayleigh damping in the shock wave propagation models. Theoretical and numerical tools and propagating models thus developed have been validated on several academic and industrial structures. Comparison with experimental data on large size industrial structures, especially a real size payload adaptor, is performed and emphasizes the coherence of our approach and the reliability and the efficiency of the proposed propagating models.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-07-21T12:20:27Z No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-09T13:15:43Z (GMT) No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) / Made available in DSpace on 2017-08-09T13:15:43Z (GMT). No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) Previous issue date: 2013-07-25 / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / Muitos compostos lamelares, como os hidróxidos duplos lamelares e os hidroxissais lamelares, vem ganhando cada vez mais atenção devido às suas inúmeras aplicabilidades no ramo de catálise, troca iônica e precursores para óxidos. Os dois compostos estudados aqui possuem sítios octaédricos e tetraédricos de zinco, sendo classificados por Louër et al. como hidroxissais do tipo II. O hidroxicloreto de zinco (Zn5(OH)8Cl2.H2O) é romboédrico e possui ocorrência natural sendo designado como simonkolleite. Enquanto que o hidroxinitrato de zinco diidratado (Zn5(OH)8(NO3)2.2H2O) é monoclínico e não possui ocorrência natural. Seus nitratos não se encontram coordenados aos zincos tetraédricos, como é o caso do composto Zn5(OH)8Cl2.H2O. Ao invés disso, suas moléculas de água se encontram coordenadas nos tetraedros e, para balancear a carga positiva das lamelas, esses nitratos se encontram na região interlamelar. Esses dois hidroxissais e uma modificação do hidroxinitrato de zinco com moléculas de amônia coordenadas aos tetraedros (BENARD, 1995) foram estudados por simulação computacional. O pacote Quantum ESPRESSO, baseado na Teoria do Funcional da Densidade (DFT – Density Functional Theory) com funções de onda planas e condições periódicas de contorno foi utilizado para a condução dos cálculos. As moléculas de água foram retiradas das estruturas hidratadas otimizadas e essas foram reotimizadas. Todos os dados experimentais foram comparados com os dados retirados das estruturas simuladas e um bom acordo foi obtido. A estrutura simulada do composto desidratado de Zn5(OH)8(NO3)2.2H2O não correspondeu à estrutura obtida pelo processo de calcinação, como foi visto pela análise termodinâmica do processo de desidratação. Porém, pôde ser concluído que essa estrutura corresponde ao mínimo local, pela ausência de frequências imaginárias. Cálculos de pós-processamento puderam ser conduzidos para uma análise das interações existentes nos compostos e das espécies químicas presentes neles. Os cloretos e os nitratos de ambos os compostos se mostraram equivalentes quimicamente, como foi visto pelo cálculo de pDOS (projected Density of States). As hidroxilas das células unitárias puderam também ser classificadas em dois grupos a partir de suas semelhanças químicas. Pôde-se concluir também com esse trabalho que o modelo de diminuição da célula unitária (DEYSE, 2012) foi capaz de diminuir os custos computacionais e prever certas propriedades dos compostos estudados. / Many layered compounds, like the double hydroxides and the hydroxide salts, have been gaining attention lately due to their various applicabilities in catalysis, anionic exchange and oxide precursors. The studied compounds here have octahedral and tetrahedral sites, which have been classified as type-2 hydroxide salts by Louër et al. Zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2.H2O) is rhombohedric and is found in the nature as a mineral so-called simonkolleite. Whereas zinc hydroxide nitrate dihydrate (Zn5(OH)8(NO3)2.2H2O) is monoclinic and does not have natural occurrence. Their nitrates are not coordinated to the tetrahedral zincs, whereas the chlorides of Zn5(OH)8Cl2.H2O are grafted to the tetrahedral zincs. Their water molecules are grafted to the tetrahedrons and, in order to balance the charges, the nitrates are located in the interlayer region. Those hydroxide salts and a modification of the zinc hydroxide nitrate with ammonia molecules grafted to the tetrahedros (BENARD, 1995) have been studied by computational simulation. The Quantum ESPRESSO package based in the Density Functional Theory (DFT) with waveplanes and periodic boundary conditions was used for the calculations. The water molecules were removed from the optimized hydrate structures and, later on, those were re-optmized. All the experimental data were compared with the ones obtained by simulated structures and a good agreement was shown. The simulated dehydrate structure of Zn5(OH)8(NO3)2.2H2O did not correspond to the structure obtained by calcination, as it was shown by the thermodynamical analysis of the calcination process. However, it was concluded that this structure corresponds to a local minimum due to the lack of imaginary frequencies. Post-processing calculations were conducted in order to analyze the compounds' interactions and the chemical species. The chlorides and nitrates of both compounds were chemically equivalents, as it was shown by the pDOS calculations (projected Density of States). The hydroxyls of the unit cells could be classified in two groups based on their chemical equivalence. It could also be concluded with this work that the unit cell reduction method (DEYSE, 2012) was able to reduce the computational costs and to predict certain properties of the studied compounds.

This thesis consists of two parts. The first part deals with the magnetic properties of Fe3O4 nanocrystals and their possible application in water remediation. The second part is on the delamination of layered materials and the preparation of new layered hybrids from the delaminated sheets. In recent years, nanoscale magnetic particles have attracted considerable attention because of their potential applications in industry, medicine and environmental remediation. The most commonly studied magnetic nanoparticles are metals, bimetals and metal oxides. Of these, magnetite, Fe3O4, nanoparticles have been the most intensively investigated as they are, non-toxic, stable and easy to synthesize. Magnetic properties of nanoparticles such as the saturation magnetization, coercivity and blocking temperature are influenced both by size and shape. Below a critical size magnetic particles can become single domain and above a critical temperature (T B , the blocking temperature) thermal fluctuations can induce random flipping of magnetic moments resulting in loss of magnetic order. At temperatures above the blocking temperature the particles are superparamagnetic. Magnetic nanocrystals of similar dimensions but with different shapes show variation in magnetic properties especially in the value of the blocking temperature, because of differences in the surface anisotropy contribution. The properties of magnetic nanoparticles are briefly reviewed in Chapter 1. The objective of the present study was to synthesize Fe3O4 nanocrystals of different morphologies, to understand the difference in magnetic properties associated with shape and to explore the possibility of using Fe3O4 nanocrystals in water remediation. In the present study, oleate capped magnetite (Fe3O4) nanocrystals of spherical and cubic morphologies of comparable dimensions (∼10nm) have been synthesized by thermal decomposition of FeOOH in high-boiling octadecene solvent (Chapter 2). The nanocrystals were characterized by XRD, TEM and XPS spectroscopy. The nanoparticles of different morphologies exhibit very different blocking temperatures. Cubic nanocrystals have a higher blocking temperature (T B = 190 K) as compared to spheres (T B = 142 K). From the shift in the hysteresis loop it is demonstrated that the higher blocking temperature is a consequence of exchange bias or exchange anisotropy that manifests when a ferromagnetic material is in physical contact with an antiferromagnetic material. In nanoparticles, the presence of an exchange bias field leads to higher blocking temperatures T B because of the magnetic exchange coupling induced at the interface between the ferromagnet and antiferromagnet. It is shown that in these iron oxide nanocrystals the exchange bias field originates from trace amounts of the antiferromagnet wustite, FeO, present along with the ferrimagnetic Fe3O4 phase. It is also shown that the higher FeO content in nanocrystals of cubic morphology is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature. Magnetic nanoparticles with moderate magnetization can be easily separated from dispersions by applying low intensity magnetic fields. Oleate capped spherical and cubic iron oxide nanocrystals have considerable magnetic moment and hence have the potential as host-carriers for magnetic separation in environmental remediation. These nanocrystals are, however, dispersible only in non-polar solvents like chloroform, toluene, etc. Environmental remediation requires that the nanocrystals be water dispersible. This was achieved by functionalizing the surface of the iron oxide nanocrystals by coordinating carboxymethyl-β-cyclodextrin (CMCD) cavities (Chapter 3). The hydroxyl groups located at the rim of the anchored cyclodextrin cavity renders the surface of the functionalized nanocrystal hydrophilic. The integrity of the anchored CMCD molecules are preserved on capping and their hydrophobic cavities available for host-guest chemistry. The CMCD capped iron oxide particles are water dispersible and separable in modest magnetic fields (<0.5 T). Small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards arsenic ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. To extend the application of the iron oxide nanocrystals so that they can both capture and destroy organic contaminants present in water, cyclodextrin functionalized water dispersible core-shell Fe3O4@TiO2 (CMCD-Fe3O4@TiO2) nanocrystals have been synthesized (Chapter 4). The application of these particles for the photocatalytic degradation of endocrine disrupting chemicals (EDC), bisphenol A and dibutyl phthalate, in water is demonstrated. EDC molecules that may be present in water are captured by the CMCD-Fe3O4@TiO2 nanoparticles by inclusion within the anchored cavities. Once included they are photocatalytically destroyed by the TiO2 shell on UV light illumination. The magnetism associated with the crystalline Fe3O4 core allows for the magnetic separation of the particles from the aqueous dispersion once photocatalytic degradation is complete. An attractive feature of these ‘capture and destroy’ nanomaterials is that they may be completely removed from the dispersion and reused with little or no loss of catalytic activity. The second part of the thesis deals with the intercalation of surfactants in inorganic layered solids and their subsequent delamination of the functionalized solid in non-polar solvents. The solids investigated were - the anionic layered double hydroxides (LDH), the 2:1 smectite clay, montmorillonite (MMT), layered metal thiophosphates (CdPS3) and graphite oxide (GO). Layered Double Hydroxides (LDH) are lamellar solids of the general chemical formula [M0(1−x)Mx(OH)2], where M0 is a divalent metal ion and M a trivalent ion. The structure of the Mg-Al layered double hydroxide (Mg-Al LDH) may be derived from that of brucite, Mg(OH)2, by isomorphous substitution of a part of the Mg2+ by trivalent Al3+ ions with electrical neutrality maintained by interlamellar exchangeable ions like nitrate or carbonate. The ion exchange intercalation of the anionic surfactant dodecyl sulfate (DDS) in an Mg-Al LDH and the subsequent delamination of the surfactant intercalated LDH in non-polar solvent is reviewed in Chapter 5. Delamination results in a clear dispersion of neutral nanosheets. The delaminated sheets are neutral as the surfactant chains remain anchored to the inorganic sheet. On solvent evaporation, the sheets re-stack to give back the original surfactant intercalated solid. This strategy for delamination of layered solids by intercalation of an appropriate surfactant followed by dispersing in a non-polar solvent has been extended to montmorillonite (MMT) and cadmium thiophosphates (CdPS3) by ion-exchange intercalation of the cationic surfactant dioctadecyldimethylammonium bromide (DODMA) followed by sonication in non-polar solvents e.g. toluene or chloroform as in the case of the LDH (Chapter 6). The nanosheets of the MMT and CdPS3 are electrically neutral as the surfactant chains remain anchored to the inorganic sheet even after exfoliation. Graphite oxide (GO) too can be delaminated by functionalizing the sheets by covalently linking oleylamine chains to the GO sheets via an amide bond. The oleylamine functionalized GO is easily delaminated in non-polar solvents to give electrically neutral GO nanosheets. It is shown in Chapter 7 that the 1:1 mixtures of dispersions of montmorillonite-DODMA with Mg-Al LDH-DDS nanosheets can self assemble, on solvent evaporation, to give a new layered solid with periodically alternating montmorillonite and LDH layers. In this method attractive forces between the neutral exfoliated nanosheets of cationic and anionic ensures self-assembly of a perfectly periodic alternating layered structure. The method has been extended to synthesize new layered solids in which surfactant tethered cationic and anionic inorganic sheets alternate. The hybrid solids synthesized are CdPS3—MgAl-LDH, CdPS3—CoAl-LDH, GO—MgAl-LDH, GO—CoAl-LDH. The procedure outlined in Chapter 7 allows for a simple, but versatile, method for generating new periodically ordered layered hybrid solids by self-assembly.

The transformation of the legacy electric grid to Smart Grid (SG) poses numerous challenges in the design and development of an efficient SG communications network. While there has been an increasing interest in identifying the SG communications network and possible SG applications, specific research challenges at the network protocol have not been elaborated yet. This dissertation revisited each layer of a TCP/IP protocol stack which basically was designed for a wired network and optimized their performance in IEEE 802.11s-based Advanced Metering Infrastructure (AMI) communications network against the following challenges: security and privacy, AMI data explosion, periodic simultaneous data reporting scheduling, poor Transport Control Protocol (TCP) performance, Address Resolution Protocol (ARP) broadcast, and network interoperability. To address these challenges, layered and/or cross-layered protocol improvements were proposed for each layer of TCP/IP protocol stack. At the application layer, a tree-based periodic time schedule and a time division multiple access-based scheduling were proposed to reduce high contention when smart meters simultaneously send their reading. Homomorphic encryption performance was investigated to handle AMI data explosion while providing security and privacy. At the transport layer, a tree-based fixed Retransmission Timeout (RTO) setting and a path-error aware RTO that exploits rich information of IEEE 802.11s data-link layer path selection were proposed to address higher delay due to TCP mechanisms. At the network layer, ARP requests create broadcast storm problems in IEEE 802.11s due to the use of MAC addresses for routing. A secure piggybacking-based ARP was proposed to eliminate this issue. The tunneling mechanisms in the LTE network cause a downlink traffic problem to IEEE 802.11s. For the network interoperability, at the network layer of EPC network, a novel UE access list was proposed to address this issue. At the data-link layer, to handle QoS mismatch between IEEE 802.11s and LTE network, Dual Queues approach was proposed for the Enhanced Distributed Channel Access. The effectiveness of all proposed approaches was validated through extensive simulation experiments using a network simulator. The simulation results showed that the proposed approaches outperformed the traditional TCP/IP protocols in terms of end to end delay, packet delivery ratio, throughput, and collection time.

再生可能エネルギーの大量導入に向けて、電力需給の安定化を目的として蓄電池を用いる電力貯蔵技術に注目が集まっている。現状のリチウムイオン電池(LIB)がベースの先進LIBは250Wh/kgの高エネルギー密度を有し、自動車のみならず電力貯蔵用途としても普及が期待されている。本研究では先進LIB正極材料として期待されるリチウム過剰系正極と高ニッケル三元系正極について容量低下などの劣化要因を明確にして、それら課題に対して正極粒子への酸化物修飾による解決を検討した。 / The development of energy storage technologies using batteries has attracted much attention to introduce the renewable energy. If we can achieve 250 Wh kg-1 with the advanced LIBs based on the principle of LIB, we can lower the cost of the total energy storage systems while ensuring the safety, and hence the advanced LIBs will accelerate the world-wide spread of large-scale power storage systems. In this thesis, the author focused surface modification of lithium-rich layered ternary transition metal oxide and high-nickel layered ternary transition metal oxide cathode particles with oxides as mitigation methods for capacity fading. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

The thesis is concerned with the contact mechanics behaviour of non-conforming solids. The geometry of the solids considered gives rise to various contact configurations, from concentrated contacts with circular and elliptical configuration to those of finite line nature, as well as those of less concentrated form such as circular flat punches. The radii of curvature of mating bodies in contact or impact give rise to these various nonconforming contact configurations and affect their contact characteristics, from those considered as semi-infinite solids in accord with the classical Hertzian theory to those that deviate from it. Furthermore, layered solids have been considered, some with higher elastic modulus than that of the substrate material (such as hard protective coatings) and some with low elastic moduli, often employed as tribological coatings (such as solid lubricants). Other bonded layered solids behave in viscoelastic manner, with creep relaxation behaviour under load, and are often used to dampen structural vibration upon impact. Analytic models have been developed for all these solids to predict their contact and impact behaviour and obtain pressure distribution, footprint shape and deformation under both elastostatic and transient dynamic conditions. Only few solutions for thin bonded layered elastic solids have been reported for elastostatic analysis. The analytical model developed in this thesis is in accord with those reported in the literature and is extended to the case of impact of balls, and employed for a number of practical applications. The elastostatic impact of a roller against a semi-infinite elastic half-space is also treated by analytic means, which has not been reported in literature. Two and three-dimensional finite element models have been developed and compared with all the derived analytic methods, and good agreement found in all cases. The finite element approach used has been made into a generic tool for all the contact configurations, elastic and viscoelastic. The physics of the contact mechanical problems is fully explained by analytic, numerical and supporting experimentation and agreement found between all these approaches to a high level of conformance. This level of agreement, the development of various analytical impact models for layered solids and finite line configuration, and the development of a multi-layered viscoelastic transducer with agreed numerical predictions account for the main contributions to knowledge. There are a significant number of findings within the thesis, but the major findings relate to the protective nature of hard coatings and high modulus bonded layered solids, and the verified viscoelastic behaviour of low elastic modulus compressible thin bonded layers. Most importantly, the thesis has created a rational framework for contact/impact of solids of low contact contiguity.

Lithium-rich layered transition metal oxide cathode, represented as the chemical formula of xLi₂MnO₃ &middot; (1 - x)LiMO₂(M = Mn, Ni, Co) , retains immense interest as one of the most promising candidates for energy storage system ranging from mobile devices to electric vehicle applications (EV/HEV/PHEV). This battery type benefits from superior theoretical capacity (&gt;250 mAhg^-1), high chemical potential (&gt;4.6 V vs Li⁰), good thermal stability, high discharge capacity and lower cost compared with conventional cathodes (e.g. LiCoO₂, Li(Ni_1/3Mn_1/3Co_1/3)O₂ cathodes). However, there remain major barriers which still need to be improved in order to achieve a successful commercialization for large-scale devices or electric vehicle applications. The irreversible capacity loss of 40-100 mAhg^-1 during the initial electrochemical cycle and the battery fading phenomena (capacity fading/voltage decay) on further cycles are the major problems which have emerged. The Li⁺ ion extraction accompanied by oxygen release from the active material in the form of oxide known as lithia (Li₂O) along with the transition metal migration has been suggested as the dominant processes underlying the capacity fading mechanism. Those processes, in turn, cause a phase transition from a layered structure into a spinel within the electrode material. The interplay of the local atomic environments between Li₂MnO₃ (monoclinic, C2/m) and LiMO₂ (trigonal/hexagonal, R3m) holds the key to developing better cathodes with enhanced stability. In the present thesis, an in operando XAS study using a specially-designed cell of the graphene- coated Li(Li_0.2Mn_0.54Ni_0.13Co_0.13)O₂ cathode is employed to examine the chemical, electronic, and structural states of the transition metals (Mn, Co, and Ni) during electrochemical cycle(s). Precise oxidation states for the transition metals is evaluated by the combined analyses from the XANES and SQUID measurements. The K-edge XANES spectral shift is quantified to investigate the contribution to the charge compensation mechanism by the oxidation change. Absorption features in K-edge XANES are identified. These features describe the electronic state of the individual atoms in the cathode composite, as well as the local distortion from the octahedral structure of MO₆. The Fourier transform of EXAFS offers a satisfactory description of the local structure changes with the connection to the cation arrangement. The description is generally involved with the peak amplitude, position, shape changes (trend), and coordination numbers in the real space. Hence, similarities or discrepancies in the local atomic environments could be compared at different state of charge. Major structural parameters are deduced from the EXAFS fitting process. These parameters can be used to distinguish different atomic environments upon voltage bias levels or investigate the appearance of the Jahn-Teller effect. A new approach to understand the atomic environment upon charge-discharge is demonstrated, namely, a Continuous Cauchy Wavelet Transform (CCWT) which enables the visualization of the EXAFS spectra in three dimensions by decomposing the k-space and R-space (uncorrected for phase shift) signals. The wavelet transform analysis provides possible evidence of the precursor that leads to the spinel phase transition in this battery system.

<p>In this study, we developed and improved the numerical mode matching (NMM) method which has previously been shown to be a fast and robust semi-analytical solver to investigate the propagation of electromagnetic (EM) waves in an isotropic layered medium. The applicable models, such as cylindrical waveguide, optical fiber, and borehole with earth geological formation, are generally modeled as an axisymmetric structure which is an orthogonal-plano-cylindrically layered (OPCL) medium consisting of materials stratified planarly and layered concentrically in the orthogonal directions.</p><p>In this report, several important improvements have been made to extend applications of this efficient solver to the anisotropic OCPL medium. The formulas for anisotropic media with three different diagonal elements in the cylindrical coordinate system are deduced to expand its application to more general materials. The perfectly matched layer (PML) is incorporated along the radial direction as an absorbing boundary condition (ABC) to make the NMM method more accurate and efficient for wave diffusion problems in unbounded media and applicable to scattering problems with lossless media. We manipulate the weak form of Maxwell's equations and impose the correct boundary conditions at the cylindrical axis to solve the singularity problem which is ignored by all previous researchers. The spectral element method (SEM) is introduced to more efficiently compute the eigenmodes of higher accuracy with less unknowns, achieving a faster mode matching procedure between different horizontal layers. We also prove the relationship of the field between opposite mode indices for different types of excitations, which can reduce the computational time by half. The formulas for computing EM fields excited by an electric or magnetic dipole located at any position with an arbitrary orientation are deduced. And the excitation are generalized to line and surface current sources which can extend the application of NMM to the simulations of controlled source electromagnetic techniques. Numerical simulations have demonstrated the efficiency and accuracy of this method.</p><p>Finally, the improved numerical mode matching (NMM) method is introduced to efficiently compute the electromagnetic response of the induction tool from orthogonal transverse hydraulic fractures in open or cased boreholes in hydrocarbon exploration. The hydraulic fracture is modeled as a slim circular disk which is symmetric with respect to the borehole axis and filled with electrically conductive or magnetic proppant. The NMM solver is first validated by comparing the normalized secondary field with experimental measurements and a commercial software. Then we analyze quantitatively the induction response sensitivity of the fracture with different parameters, such as length, conductivity and permeability of the filled proppant, to evaluate the effectiveness of the induction logging tool for fracture detection and mapping. Casings with different thicknesses, conductivities and permeabilities are modeled together with the fractures in boreholes to investigate their effects for fracture detection. It reveals that the normalized secondary field will not be weakened at low frequencies, ensuring the induction tool is still applicable for fracture detection, though the attenuation of electromagnetic field through the casing is significant. A hybrid approach combining the NMM method and BCGS-FFT solver based integral equation has been proposed to efficiently simulate the open or cased borehole with tilted fractures which is a non-axisymmetric model.</p> / Dissertation

The technology of semiconductor-based photocatalytic water splitting to produce hydrogen using solar energy has been considered as one of the most important approaches to solve the world energy crisis. Therefore, the development of the effective semiconductor photocatalysts has undergone considerable research. However, the traditional photocatalysts suffer from the negative effects from rapid charge recombination, which reduces the excited charges by emitting light or generating phonons. Efficient charge separation and fast charge transport, avoiding any bulk/surface recombination, are fundamentally important for photocatalytic hydrogen generation through water splitting. Here, we have introduced assembled layered materials as photocatalyst systems with their unique physicochemical properties to realize the effective charge separation and high photocatalytic activity. Using graphene as a two-dimensional supporting matrix, we have succeeded in selective anchoring of semiconductor and metal nanoparticles as separate catalytically active sites on the graphene surface. The ability of graphene to capture, transfer and store electrons and its potential to serve as a conductive support are demonstrated. The TiO₂ semiconductor/metals nanocrystals-graphene ensemble makes it possible to carry out selective catalytic processes at the separate sites and provides the potentials for applications in water splitting reactions. After demonstrating the positive role of graphene in such photocatalytic system, we then fabricate a simple but highly cooperative ensemble with CdS and MoS₂ nanocrystals dispersed on graphene sheets. It is demonstrated that CdS nanocrystals can also capture visible light energy and facilitate excited electron transfer to MoS₂ (as metal substituent) for catalytic hydrogen production via the 2-D graphene which plays a key role as an efficient electron mediator. Hexagonal multilayer MoS₂ with a layered structure in this system serves to provide active sites for hydrogen evolution by its exposed Mo edges. Hence, multilayer MoS₂ is an ideal cocatalyst of semiconductors for hydrogen generation. This crystalline-layered structure also shows semiconducting properties, however, its characteristic indirect band gap displays a poor light capture and emission ability with excited electrons and holes with different momentum. In contrast, single layer MoS₂ shows a direct band gap behavior. Our studies have clearly shown that single layer MoS₂ prepared with lithium intercalation indeed displays encouraging results in hydrogen evolution due to the direct band gap and quantum confinement effects. In addition, the exfoliated single layer MoS₂ exhibits extraordinary enhanced activity and stability in combination with the Eosin Y sensitized system when compared to those of multilayer MoS₂ and bulk MoS₂ counterparts, which is attributed to the improvement of the density of surface active sites with stronger adsorption for the Eosin Y molecules on the single layer MoS₂. In addition, this multifunctional catalyst on graphene sheet can also create adsorption sites on a defective basal surface of single layer MoS₂ through adsorption of Eosin Y where electron transfer from photoexcited Eosin Y molecule to graphene via the 2-D MoS₂ mainly takes place. Thus, the photo-generated electrons are then effectively transported to the exposed active sites of MoS₂ for the proton reduction to hydrogen molecule. It is believed the above novel assembled molecular layered systems may be applicable for a wide range of catalytic,photocatalytic and electrocatalytic reactions.