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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Poluições da água e do solo são duas das cinco categorias básicas de poluição ambiental. As outras três são do ar, ruído e luz. Poluição ocorre quando um material/produto químico é adicionado ao meio ambiente afetando-o adversamente. Uma vez que a poluição existe, retornar a matriz impactada para o seu estado anteriormente não poluído torna-se muito difícil ou até mesmo impossível em alguns casos. Os compostos organoclorados (OC) representam um importante grupo de poluentes orgânicos persistentes (POP), devido à sua toxicidade e elevada persistência no ambiente. Diferentes técnicas de remediação de solo e água subterrânea têm sido desenvolvidas com o objetivo de reparar as áreas contaminadas em menor tempo e custo possíveis e, assim, a oxidação química in situ tem se mostrado uma técnica cada vez mais atraente devido sua simplicidade e baixo custo. A degradação de dois compostos organoclorados via oxidação química por reagente de Fenton em solução aquosa é o objeto do presente trabalho. Para tanto, foram selecionados dois compostos, sendo um alifático e outro aromático. Assim, foram avaliadas as condições de degradação dos compostos organoclorados em relação às concentrações do oxidante em diferentes tempos reacionais, diferentes fontes de catalisador e, de forma qualitativa, quais foram os principais subprodutos formados. Os ensaios oxidativos foram realizados em meio aquoso com temperatura controlada a 25 C e em 3 configurações de [Fe2+] e [H2O2]. A extração dos compostos de interesse para a fase orgânica também foi estudada. A análise dos extratos revelou que o acetato de etila foi o solvente que melhor extraiu os compostos de interesse da fase aquosa. Além destes ensaios, foram avaliadas outras duas fontes de Fe(II), sendo 11 óxidos de manganês dopados com ferro e a classe de solo predominante no território nacional, que é caracterizada pela sua alta concentração de ferro endógeno (latossolo). O ensaio entre as fontes de ferro revelou que tanto o óxido de Mn quanto o latossolo produziram menos subprodutos em relação à reação com a solução de sulfato Fe(II). Entretanto, em termos quantitativos, a redução na concentração de clorobenzeno foi mais efetiva na reação com a solução de Fe(II) (cerca de 63%). A identificação dos sobprodutos foi realizada a partir da análise em cromatógrafo a gás acoplado a espectrômetro de massas e em análise comparativa dos espectros com a biblioteca NIST. Os ensaios oxidativos revelaram que em baixas concentrações de oxidante, há a possibilidade de geração de subprodutos mais tóxicos que os reagentes, sendo produzido bifenilas policloradas e hexaclorociclohexano nas reações com clorobenzeno e 1,2-dicloroetano, respectivamente

Rechargeable Li-ion batteries and supercapacitors are the most promising electrochemical energy storage devices in terms of energy density and power density, respectively. Recently, nanostructured materials have gained enormous interest in the field of energy technology as they have special properties compared to the bulk. Commercially available Li-ion batteries, which are the most advanced among the rechargeable batteries, utilize microcrystalline transition metal oxides as cathode materials which act as lithium insertion hosts. To explore better electrochemical performance the use of nanomaterials instead of conventional materials would be an excellent alternative. High Li-ion insertion at high discharge rates causes slow Li+ transport which in turn results in concentration polarization of lithium ions within the electrode material, causing a drop in cell voltage. This eventually, leads in termination of the discharge process before realizing the maximum capacity of the electrode material being used. This problem can be addressed by decreasing the average particle size which leads to an increase in surface area of the electrode material. Nanostructured materials, because of their high surface area and large surface to volume ratio, to some extent can overcome the problem of slow diffusion of ions. Supercapacitors are electrical energy storage devices which can deliver large energy in a short time. A supercapacitor can be used as an auxiliary energy device along with a primary source such as a battery or a fuel cell to achieve power enhancement in short pulse applications. Active materials for supercapacitors are classified into three categories: (i) carbonaceous materials, (ii) conducting polymers and (iii) metal oxides. Among the materials studied over the years, metal oxides have been considered as attractive electrode materials for supercapacitors due to the following merits: variable oxidation state, good chemical and electrochemical stability, ease of preparation and handling. The performance of supercapacitors can be enhanced by moving from bulk to nanostructured materials. The theme of the thesis is to explore novel routes to synthesize nanostructured materials for Li-ion batteries and supercapacitors, and to investigate their physical and electrochemical characteristics. Chapter I is an introduction of various types of electrochemical energy systems such as battery, fuel cell and supercapacitor. A brief review is made on electrode materials for Li-ion batteries and supercapacitors, and nanostructured materials. Chapter II deals with the study of nanostrip orthorhombic V2O5 synthesized by a two-step procedure, with the formation of a vanadyl ethylene glycolate precursor and post-calcination treatment. The precursor and the final product are characterized for phase and composition by powder X-ray diffraction (XRD), infrared (IR) spectroscopy, thermal analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The morphological changes are investigated using field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HRTEM). It is found that the individual strips have the following dimensions, length: 1.3 μm, width: 332 nm and thickness: 45 nm. The electrochemical lithium intercalation and de-intercalation of nanostrip V2O5 is investigated by cyclic voltammetry (CV), galvanostatic charge-discharge cycling, galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy. Chapter III describes the synthesis of nanoparticels of LiMn2O4 by microwave assisted hydrothermal method. The phase and purity of spinel LiMn2O4 are confirmed by powder XRD analysis. The morphological studies are carried out using FE-SEM and HRTEM. The electrochemical performance of spinel LiMn2O4 is studied by using CV and galvanostatic charge-discharge cycling. The initial discharge capacity is found to be about 89 mAh g-1 at a current density of 21 mA g-1 with reasonably good cyclability. Chapter IV deals with synthesis of MoO2 nanoparticles through ethylene glycol medium and its electrochemical characterization. XRD data confirms the formation MoO2 on monoclinic phase, space group P21/c. Polygon shape of MoO2 is observed in HRTEM. MoO2 facilitates reversible insertion-extraction of Li+ ions between 0.25 to 3.0 V vs. Li/Li+. CV and galvanostatic charge-discharge cycling are conducted on this anode material to complement the electrochemical data. Chapter V reports the synthesis of nanostructured MnO2 at ambient conditions by reduction of potassium permanganate with aniline. Physical characterization is carried out to identify the phase and morphology. The as prepared MnO2 is amorphous and it contains particles of 5 to 10 nm in diameter. On annealing at a temperature > 400 °C, the amorphous MnO2 attains crystalline α-phase with a concomitant change in morphology. A gradual conversion of nanoparticles to nanorods (length 500-750 nm and diameter 50-100 nm) is evident from SEM and TEM studies. High resolution TEM images suggest that nanoparticles and nanorods grow in different crystallographic planes. The electrochemical lithium intercalation and de-intercalation of nanorods was performed by (CV) and galvanostatic charge-discharge cycling. The initial discharge capacity of nanorod α-MnO2 is found to be about 197 mAh g-1 at a current density of 13.0 mA g-1. Capacitance behavior of amorphous MnO2 is studied by CV and galvanostatic charge-discharge cycling in a potential range from -0.2 to 1.0 V vs. SCE in 0.1 M sodium sulphate solution. The effect of annealing on specific capacitance is also investigated. Specific capacitance of about 250 F g-1 is obtained for as prepared MnO2 at a current density of 0.5 mA cm-2 (0.8 A g-1). Chapter VI pertains to electrochemical supercapacitor studies on nanostructured MnO2 synthesized by polyol method. Although X-ray diffraction (XRD) pattern of the as synthesized nano-MnO2 shows poor crystallinity, it is found that it is locally arranged in δ-MnO2 type layered structure composed of edge-shared network of MnO6 octahedra by Mn K-edge X-ray Absorption Near Edge Structure (XANES) measurement. Annealed MnO2 shows high crystalline tunneled based α-MnO2 as confirmed by powder XRD pattern and XANES. As synthesized MnO2 exhibits good cyclability as an electrode material for supercapacitor. In Chapter VII, capacitance behavior of nanostrip V2O5, TiO2 coated V2O5 and nanocomposites of PEDOT/V2O5 are presented. Structural and morphological studies are carried out by powder XRD, IR, TGA, SEM and TEM. Cyclic voltammogram of pristine V2O5 shows the regular rectangular shape indicating the ideal capacitance behavior in aqueous 0.1 M K2SO4. The SC value of pristine V2O5 is found to be about 100 F g-1. Nanostrip V2O5 is modified with TiO2 using titanium isobutoxide to enhance the capacitance retention upon cycling. Only 48 % of the initial capacitance remains in the case of pristine V2O5 after 100 cycles, while TiO2 coated V2O5 exhibits better cyclability with capacitance of 70 % of the initial capacitance. The capacitance retention is attributed to the presence of TiO2 on the surface of V2O5 which prevents the vanadium dissolution into the electrolyte. Microwave assisted hydrothermally synthesized PEDOT/V2O5 nanocomposites are utilized as capacitor materials. The initial SC of PEDOT/V2O5 (237 F g-1) is higher than that of either pristine V2O5 or PEDOT. The enhanced electrochemical performance is attributed to synergic effect and an enhanced bi-dimensionality. Details of the above studies are described in the thesis with a conclusion at the end of each Chapter.

Cette étude concerne le développement de nanoparticules hybrides offrant de nouvelles stratégies pour la thérapie et le diagnostic médical. Elles sont constituées d’un cœur magnétique jouant le rôle d’agent de contraste pour l’IRM et d’inducteur de chaleur par hyperthermie, d’une couronne de polymère thermosensible permettant d’encapsuler des principes actifs et de peptides de reconnaissance biologique. Une grande partie de l’étude a consisté à étudier les processus d'adsorption de copolymères poly(éther)-b-poly(L-lysine) de composition variable sur les particules magnétiques et à comprendre le rôle de la conformation des chaînes polymère à la surface des particules sur la stabilité des colloïdes en milieu physiologique. Un agent antitumoral a été encapsulé puis libéré de façon contrôlée sous l’effet d’un champ magnétique alternatif en exploitant le caractère thermosensible des blocs polyéthers. Des séquences peptidiques ciblant les zones d’inflammation de la barrière hémato-encéphalique ont été greffées sur les copolymères. L’efficacité du ciblage a été validée par IRM et fluorescence sur un modèle animal démontrant ainsi la multifonctionnalité des nanoparticules. / This work deals with the development of hybrid nanoparticles that could offer new strategies for therapy and diagnostic. These are based on a magnetic core which can play the role of contrast agent for MRI as well as heat inductor in AC magnetic field. This inorganic core is surrounded by a thermo-responsive polymeric brush that controls the loading and the release of drugs, and can be functionalized by specific ligands ensuring the targeting specificity. A large part of this work consists in studying the adsorption mechanism of poly(ether)-b-poly(L-lysine) based block copolymers onto magnetic particle and to better understand the influence of the polymer chain conformation at particles surface on the colloidal stability under physiological conditions. An anticancer drug has been loaded and released in a controlled manner under alternative magnetic field by taking advantage from the thermosensitivity of the polyether block. Targeting peptides specific of inflammation sites at the blood brain barrier have been grafted onto copolymers. The targeting specificity has been demonstrated by MRI and fluorescence imaging in rats attesting the multifunctionality of such nanoparticles.

Les estimations précises des états de charge (« State of Charge » - SoC) et de santé (« State of Health » - SoH) des batteries au lithium sont un point crucial lors d’une utilisation industrielle de celles-ci. Ces estimations permettent d’améliorer la fiabilité et la robustesse des équipements embarquant ces batteries. Cette thèse CIFRE est consacrée à la recherche d’algorithmes de détermination de l’état de santé de batteries lithium-ion, en particulier de chimie Lithium Fer Phosphate (LFP) et Lithium Manganèse Oxyde (LMO).Les recherches ont été orientées vers des solutions de détermination du SoH directement embarquables dans les calculateurs des véhicules électriques. Des contraintes fortes de coût et de robustesse constituent ainsi le fil directeur des travaux.Or, si la littérature actuelle propose différentes solutions de détermination du SoH, celles embarquées ou embarquables sont encore peu étudiées. Cette thèse présente donc une importante revue bibliographique des différentes méthodes d’estimation du SoH existantes, qu’elles soient embarquables ou non. Le fonctionnement détaillé ainsi que les mécanismes de vieillissement d’une batterie lithium-ion sont également explicités.Une partie majoritaire des travaux est consacrée à l’utilisation de l’analyse incrémentale de la capacité (« Incremental Capacity Analysis » - ICA) en conditions réelles, c’est-à-dire avec les niveaux de courant présents lors d’un profil de mission classique d’un véhicule électrique, avec les mesures disponibles sur un BMS (« Battery Management System ») industriel et avec les contraintes de robustesses associées, notamment une gamme étendue de température de fonctionnement. L’utilisation de l’ICA pour déterminer la capacité résiduelle de la batterie est mise en œuvre de façon totalement innovante et permet d’obtenir une grande robustesse aux variations des conditions d’utilisation de la batterie.Une seconde méthode est, elle, dédiée à la chimie LMO et exploite le fait que le potentiel aux bornes de la batterie soit représentatif de son état de charge. Un compteur coulométrique partiel est ainsi proposé, intégrant une gestion dynamique des bornes d’intégration en fonction de l’état de la batterie.A l’issue des travaux, une méthode complète et précise de détermination du SoH est disponible pour chacune des chimies LFP et LMO. La détermination de la capacité résiduelle de ces deux familles de batteries est ainsi possible à 4 % près. / Accurate lithium-ion battery State of Charge (SoC) and State of Health (SoH) estimations are nowadays a crucial point, especially when considering an industrial use. These estimations enable to improve robustness and reliability of hardware using such batteries. This thesis focuses on researching lithium-ion batteries state of health estimators, in particular considering Lithium Iron Phosphate (LFP) and Lithium Manganese Oxide (LMO) chemistries.Researches have been targeted towards SoH estimators straight embeddable into electric vehicles (EV) computers. Cost and reliability constraints are thus the main guideline for this work.Although existing literature offers various SoH estimators, those who are embedded or embeddable are still little studied. A complete literature review about SoH estimators, embedded or not, is therefore proposed. Lithium-ion batteries detailed operation and ageing mechanisms are also presented.The main part of this work is dedicated to Incremental Capacity Analysis (ICA) use with electric vehicle constraints, such as current levels available with a typical EV mission profile or existing measurements on the Battery Management System (BMS). Incremental Capacity Analysis is implemented in an innovative way and leads to a remaining capacity estimator with a high robustness to conditions of use variations, including an extended temperature range.A second method, dedicated to LMO chemistry, take advantage of the fact that the battery potential is representative of its state of charge. Partial Coulomb counting is thus performed, with a dynamic management of integration limits, depending on the battery state.Outcomes of this work are two complete and accurate SoH estimators, one for each chemistry, leading to a remaining capacity estimation accurate within 4 %.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Poluições da água e do solo são duas das cinco categorias básicas de poluição ambiental. As outras três são do ar, ruído e luz. Poluição ocorre quando um material/produto químico é adicionado ao meio ambiente afetando-o adversamente. Uma vez que a poluição existe, retornar a matriz impactada para o seu estado anteriormente não poluído torna-se muito difícil ou até mesmo impossível em alguns casos. Os compostos organoclorados (OC) representam um importante grupo de poluentes orgânicos persistentes (POP), devido à sua toxicidade e elevada persistência no ambiente. Diferentes técnicas de remediação de solo e água subterrânea têm sido desenvolvidas com o objetivo de reparar as áreas contaminadas em menor tempo e custo possíveis e, assim, a oxidação química in situ tem se mostrado uma técnica cada vez mais atraente devido sua simplicidade e baixo custo. A degradação de dois compostos organoclorados via oxidação química por reagente de Fenton em solução aquosa é o objeto do presente trabalho. Para tanto, foram selecionados dois compostos, sendo um alifático e outro aromático. Assim, foram avaliadas as condições de degradação dos compostos organoclorados em relação às concentrações do oxidante em diferentes tempos reacionais, diferentes fontes de catalisador e, de forma qualitativa, quais foram os principais subprodutos formados. Os ensaios oxidativos foram realizados em meio aquoso com temperatura controlada a 25 C e em 3 configurações de [Fe2+] e [H2O2]. A extração dos compostos de interesse para a fase orgânica também foi estudada. A análise dos extratos revelou que o acetato de etila foi o solvente que melhor extraiu os compostos de interesse da fase aquosa. Além destes ensaios, foram avaliadas outras duas fontes de Fe(II), sendo 11 óxidos de manganês dopados com ferro e a classe de solo predominante no território nacional, que é caracterizada pela sua alta concentração de ferro endógeno (latossolo). O ensaio entre as fontes de ferro revelou que tanto o óxido de Mn quanto o latossolo produziram menos subprodutos em relação à reação com a solução de sulfato Fe(II). Entretanto, em termos quantitativos, a redução na concentração de clorobenzeno foi mais efetiva na reação com a solução de Fe(II) (cerca de 63%). A identificação dos sobprodutos foi realizada a partir da análise em cromatógrafo a gás acoplado a espectrômetro de massas e em análise comparativa dos espectros com a biblioteca NIST. Os ensaios oxidativos revelaram que em baixas concentrações de oxidante, há a possibilidade de geração de subprodutos mais tóxicos que os reagentes, sendo produzido bifenilas policloradas e hexaclorociclohexano nas reações com clorobenzeno e 1,2-dicloroetano, respectivamente

Philosophiae Doctor - PhD

Nous présentons une étude des effets de contrainte induits par l’épitaxie dans des couches minces La1-xSrxMnO3 (LSMO) (001) (x = 0.33) pour 3 épaisseurs de films (50, 25 et 12 nm) déposés par Ablation Laser Pulsée (PLD) sur différents substrats tels que SrTiO3 (STO) (001), STO buffered MgO (001), NdGaO3 (NGO) (110) et (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) (001). L’étude est complétée par l’effet de la composition sur les propriétés magnétiques de couches minces de La1-xSrxMnO3 avec x=0,33 et 0,38 déposées par Epitaxie à Jets Moléculaires (MBE). Des caractérisations par diffraction de rayons X (XRD), et microscopie à force atomique (AFM), des mesures de résistivité électrique en quatre points en fonction de la température, d’aimantation par magnetometrie à SQUID (Superconducting Quantum Interference Device) et d’anisotropie magnétique par magnétométrie magnéto-optique Kerr vectorielle (MOKE) sont présentées. Les évolutions angulaires de l’anisotropie magnétique, de l’aimantation à rémanence, du champ coercitif et du champ de renversement d’aimantation ont ainsi pu être analysées pour des films épitaxiés LSMO de différentes épaisseurs. Des études en fonction de la température complètent les données. L’origine de l’anisotropie (magnétique, magnétocristalline, magnétostrictive ou liée aux effets de marches et d’angle de désorientation du substrat) est finalement discutée. / We report a quantitative analysis of thickness dependent epitaxial strain-induced effects in La1-xSrxMnO3 (LSMO) (001) (x = 0.33) thin films of thicknesses (50, 25 and 12 nm) grown on various single crystal substrates such as SrTiO3 (STO) (001), STO buffered MgO (001), NdGaO3 (NGO) (110) and (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) (001) by Pulsed Laser Deposition (PLD) technique. We also report the composition dependent magnetic properties of LSMO thin films with x = 0.33 and 0.38 in particular grown onto LSAT (001) substrate by Molecular Beam Epitaxy (MBE). The study mainly includes measurements such as X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), temperature dependent four-probe resistivity, magnetization properties by Superconducting Quantum Interference Device (SQUID), magnetic anisotropy by Magneto-Optical Kerr Magnetometry (MOKE). Our results highlight the detailed study of angular evolution and thickness dependent magnetic anisotropy, remanence, coercivity and switching field in epitaxial LSMO thin films. Temperature-dependent studies are also performed on few selected films. We will also discuss the cause of magnetic anisotropy in LSMO films i.e., magneto-crystalline and magnetostriction anisotropy and the effects of steps or substrate mis-cut induced anisotropy.

Coordination complexes [M(O2CCH2OC2H4OMe)2] (M = Co, 4; M = Mn, 5) are accessible by the anion exchange reaction between the corresponding metal acetates [M(OAc)2(H2O)4] (M = Co, 1; M = Mn, 2) and the carboxylic acid HO2CCH2OC2H4OMe (3). IR spectroscopy confirms the chelating or μ-bridging binding mode of the carboxylato ligands to M(II). The molecular structure of 5 in the solid state confirms a distorted octahedral arrangement at Mn(II), setup by the two carboxylato ligands including their α-ether oxygen atoms, resulting in an overall two-dimensional coordination network. The thermal decomposition behavior of 4 and 5 was studied by TG-MS, revealing that decarboxylation occurs initially giving [M(CH2OC2H4OMe)2], which further decomposes by M–C, C–O and C–C bond cleavages. Complexes 4 and 5 were used as CCVD (combustion chemical vapour deposition) precursors for the deposition of Co3O4, crystalline Mn3O4 and amorphous Mn2O3 thin films on silicon and glass substrates. The deposition experiments were carried out using three different precursor solutions (0.4, 0.6 and 0.8 M) at 400 °C. Depending on the precursor concentration, particulated layers were obtained as evidenced by SEM. The layer thicknesses range from 32 to 170 nm. The rms roughness of the respective films was determined by AFM, displaying that the higher the precursor concentration, the rougher the Co3O4 surface is (17.4–43.8 nm), while the manganese oxide films are almost similar (6.2–9.8 nm).

No description available.