This doctoral thesis deals with synthesis and characterisation of electroactive electrode materials for li-ion batteries and accumulators. The work is divided into two main parts. One deals with LiFePO4 based cathode composite electroactive material and in the second is described the synthesis and utilization of monoclinic TiO2(B) as an anode for li-ion cell. The main aim of the work is to relate the synthesis procedure and structural properties of both materials to its electrochemical preformance.

No description available.

No description available.

At present, the use of other sources of energy other than energy source from crude oil has accelerated. This is due to limited resources of fossil fuel, increasing prices of crude oil and environmental concerns. Alternative fuels such as biofuel are becoming more important because it can serve as a replacement for petroleum diesel due to its comparable fuel properties and cleaner emission. For use in a standard diesel engine, biodiesel can be blended (mixed) with petroleum diesel at any concentration. In this study, transesterification of waste cooking oil with methanol was catalyzed by heterogeneous catalyst TiO2-supported-MgO and the biodiesel produced was characterised. Waste cooking oil (WCO) was used because it is regarded as one of the cheapest feedstock for biodiesel production in that most oils from oil crops are used as food. Waste cooking oil is available in vast amounts each day in every restaurants and fast food outlets worldwide. The waste cooking oil used in this study was laboratory prepared by the addition of 5 wt. % of oleic acid into 95 wt. % of soybeans oil.10 wt. % of titanium-supported-magnesium oxide catalyst (MgO/TiO2) used was prepared by incipient wetness impregnation and characterized using XRF, BET and XRD. These materials were tested with the catalyst for the conversion of waste vegetable oil to biodiesel in presence of methanol and hexane co-solvent. Methanol to oil mole ratio of 18:1 was employed in the transesterification process. When hexane was used as cosolvent, methanol to oil mole ratio of 18:1 and methanol to hexane mole ratio of 1:1 was used. The effects of reaction time, reaction temperature and hexane co-solvent on the waste vegetable oil conversion has been established. The 1HNMR analysis was used to estimate the structure of FAME produced. It was observed that the oil conversion increases with the increased reaction time, reaction temperature and use of hexane as co-solvent. / Chemical Engineering / M. Tech. (Chemical Engineering)

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This thesis describes the synthesis and characterisation of titania photocatalysts for incorporation into a polyethylene film. Monodisperse, anatase-phase titania nanoparticles are prepared and the synthesis conditions necessary for attraction to a laponite clay support are determined. Methods of preventing agglomeration of the laponite system such as the use of a polyethylene oxide surfactant or chemical modification of the laponite plate edges with a dimethyloctyl methoxysilane are also explored. Finally, photocatalytic studies on the laponite-supported titania nanoparticles are performed, and the compatibility and photoactivity of these materials in the polyethylene film are examined.

Κατά τις τελευταίες δεκαετίες παρατηρείται συνεχής αύξηση της έντασης του φαινομένου του θερμοκηπίου γεγονός που προκαλεί σημαντικές συνέπειες στο περιβάλλον και στη ζωή μας γενικότερα. Συνεπώς, είναι απαραίτητη η μείωση της ανθρωπογενούς εκπομπής των αερίων που συμβάλλουν στην αύξηση του φαινομένου αυτού. Η εκμετάλλευση και χρήση των δύο πιο σημαντικών θερμοκηπικών αερίων, του μεθανίου και του διοξειδίου του άνθρακα, μπορεί να επιτευχθεί με την αναμόρφωση του CH4 με CO2 ή αλλιώς ξηρή αναμόρφωση του μεθανίου (Dry Reforming of Methane-DRM). Με τη διεργασία DRM τα δύο συγκεκριμένα αέρια μετατρέπονται σε αέριο σύνθεσης (synthesis gas), το οποίο χρησιμοποιείται είτε για τη σύνθεση πληθώρας οργανικών ενώσεων, είτε για την παραγωγή Η2 για ενεργειακούς σκοπούς. Η DRM παρουσιάζει σημαντικά πλεονεκτήματα: δεν απαιτείται η χρήση ύδατος, φθηνό σχετικά κόστος εγκαταστάσεων, χρησιμοποιείται σε χημικά συστήματα μεταφοράς ενέργειας, ενώ και το αέριο σύνθεσης που παράγεται έχει ακόμα κατάλληλη αναλογία για συνθέσεις Fischer–Tropsch. Παρόλα αυτά η DRM δεν έχει εκτεταμένη βιομηχανική εφαρμογή επειδή αντιμετωπίζει ένα σημαντικό μειονέκτημα: ο καταλύτης μετά από κάποιο χρόνο λειτουργίας απενεργοποιείται λόγω του άνθρακα που αποτίθεται πάνω του. Στην παρούσα εργασία μελετήθηκε ο state of the art καταλύτης Ni/Al2O3, τον οποίο τροποποιήσαμε με βόριο σε διάφορους λόγους [Β/(B+Νi)] με κύριο στόχο τη μείωση των ανθρακούχων αποθέσεων. Οι τροποποιημένοι καταλύτες συντέθηκαν με τη μέθοδο του υγρού συνεμποτισμού και χαρακτηρίστηκαν φυσικοχημικά με διάφορες τεχνικές, ώστε να μελετήσουμε την επίδραση του βορίου στην υφή τους (ΒΕΤ, porosimetry, SEM, TEM), στη δομή τους (XRD, UV-Vis DRS) και στην αναγωγιμότητά τους (H2-TPR). Η καταλυτική συμπεριφορά τους για την αντίδραση της ξηρής αναμόρφωσης του μεθανίου αξιολογήθηκε σε αντιδραστήρα σταθερής κλίνης, για 24h, σε συνθήκες: 973Κ, 1 atm, τροφοδοσία 50%CH4-50%CO2. Ο άνθρακας που αποτέθηκε στους χρησιμοποιημένους καταλύτες μετρήθηκε με τη μέθοδο της θερμοπρογραμματισμένης υδρογόνωσης (TPH). Τα ανηγμένα και χρησιμοποιημένα στην DRM καταλυτικά δείγματα μελετήθηκαν επίσης με ηλεκτρονικό μικροσκόπιο σάρωσης (SEM με αναλυτή EDS) και ηλεκτρονικό μικροσκόπιο διαπερατότητας (ΤΕΜ). Βρέθηκε ότι η παρουσία του Β μειώνει σημαντικά την ποσότητα του αποτιθέμενου άνθρακα στους καταλύτες Ni/Al2O3, σε ποσοστό έως και 86%, χωρίς να επηρεάζει ιδιαίτερα τη δραστικότητα και την εκλεκτικότητα των καταλυτών. Σημαντικό ρόλο παίζει το ποσοστό του Β στον καταλύτη, με τον καταλύτη με λόγο Β/(B+Νi) = 0,5 να εμφανίζει τη βέλτιστη συμπεριφορά. Τα αποτελέσματα μας έδειξαν ότι η ιδιαίτερη θετική επίδραση του βορίου οφείλεται κυρίως στο γεγονός ότι ευνοεί τη διασπορά του μεταλλικού νικελίου. Τροποποίηση με βόριο, σε κατάλληλη περιοχή φορτίσεων, του καταλύτη Ni/Al2O3 μεγιστοποιεί το πλήθος των νανοσωματιδίων νικελίου με μέση διάσταση < 6.0 nm, τα οποία, ως γνωστόν, ελαχιστοποιούν την απόθεση άνθρακα. / The intensity of the greenhouse effect is constantly increasing in the last few decades with an adverse effect both on the environment and the humanity. In order to decrease the effect, human-caused emissions should be minimized. The two most important greenhouse gases, methane and carbon dioxide, can be used in the DRM (Dry Reforming of Methane) process. With this process the above mentioned gases are converted to synthesis gas, which is then used for the synthesis of a great number of organic compounds and synthetic fuels (through the Fisher-Tropsch syntheses) or for the production hydrogen to be used as a fuel (energy purposes). The DRM process presents a number of advantages, namely: no water is required, relatively low cost of process plants,it can be used as a Chemical Energy Transfer System and, finally, the produced synthesis gas has adequate CO/H2 ratio for Fisher-Tropsch syntheses. Although DRM is a promising process, its industrial application is hindered by a major drawback: the catalysts are rapidly deactivating due to coking. In the current study, the state of the art catalyst Ni/Al2O3 was studied and modified with boron, using different ratios of Β/(B+Νi). Our primary objective was to reduce coking. The modified catalysts were synthesized by wet co-impregnation and physicochemically characterized in their oxidic, reduced and used forms, using various techniques, in order to investigate the influence of boron on the texture (BET, Porosimetry, SEM, TEM), structure (XRD, UV-Vis DRS) and reducibility (H2-TPR) of the catalysts. The catalytic performance for the DRM process was studied under stable conditions (973Κ, 1 atm and 50%CH4-50%CO2 undiluted feed), for 24h, using a fixed bed reactor. Carbonaceous deposits on the used catalysts were determined by Temperature Programmed Hydrogenation (TPH). Scanning Electron Microscopy (SEM) with EDS analyser and Transmission Electron Microscopy (TEM) were also used in the study of reduced and used catalytic samples. Modifying Ni/Al2O3 catalysts with boron results in a great decrease of the deposited coke (up to 86%), without any significantly influence on the activity and selectivity of the catalysts. A major factor influencing the catalyst is the B loading, with the ratio Β/(B+Νi)=0,5 giving the best results. Boron’s positive effect was mainly attributed to its ability to increase Ni dispersion. Modification of Ni/Al2O3 catalysts, by using the appropriate boron loading, resulted to an increase of the amount of nickel nanoparticles with an average dimension under 6.0 nm, which are known to minimize coke deposition.

At present, the use of other sources of energy other than energy source from crude oil has accelerated. This is due to limited resources of fossil fuel, increasing prices of crude oil and environmental concerns. Alternative fuels such as biofuel are becoming more important because it can serve as a replacement for petroleum diesel due to its comparable fuel properties and cleaner emission. For use in a standard diesel engine, biodiesel can be blended (mixed) with petroleum diesel at any concentration. In this study, transesterification of waste cooking oil with methanol was catalyzed by heterogeneous catalyst TiO2-supported-MgO and the biodiesel produced was characterised. Waste cooking oil (WCO) was used because it is regarded as one of the cheapest feedstock for biodiesel production in that most oils from oil crops are used as food. Waste cooking oil is available in vast amounts each day in every restaurants and fast food outlets worldwide. The waste cooking oil used in this study was laboratory prepared by the addition of 5 wt. % of oleic acid into 95 wt. % of soybeans oil.10 wt. % of titanium-supported-magnesium oxide catalyst (MgO/TiO2) used was prepared by incipient wetness impregnation and characterized using XRF, BET and XRD. These materials were tested with the catalyst for the conversion of waste vegetable oil to biodiesel in presence of methanol and hexane co-solvent. Methanol to oil mole ratio of 18:1 was employed in the transesterification process. When hexane was used as cosolvent, methanol to oil mole ratio of 18:1 and methanol to hexane mole ratio of 1:1 was used. The effects of reaction time, reaction temperature and hexane co-solvent on the waste vegetable oil conversion has been established. The 1HNMR analysis was used to estimate the structure of FAME produced. It was observed that the oil conversion increases with the increased reaction time, reaction temperature and use of hexane as co-solvent. / Chemical Engineering / M. Tech. (Chemical Engineering)

Cette thèse a pour but de proposer toutes les avancées possibles dans l’utilisation du modèle de propagation Multi-Resolution Frequency-Domain ParFlow (MR-FDPF). Etant un modèle de propagation radio déterministe, le modèle MR-FDPF possède un haut niveau de précision, mais souffre des limitations communes à tous les modèles déterministes. Par exemple, un canal radio réel n’est pas déterministe, mais un processus aléatoire à cause par exemple des personnes ou objets mobiles, et ne peut donc être décrit fidèlement par un modèle purement déterministe. Dans cette thèse, un modèle semi-déterministe est proposé, basé sur le modèle MR-FDPF, qui introduit une part stochastique pour tenir compte des aspects aléatoires du canal radio réaliste. La partie déterministe du modèle est composée du path loss (atténuation d’espace), et la partie stochastique venant du shadow fading (masquage) et du small scale fading (évanouissement). De même, de nombreux simulateurs de propagation radio ne proposent que la prédiction de la puissance moyenne. Mais pour une simulation précise de la propagation radio il convient de prédire également des informations de fading permettant dès lors une prédiction précise du taux d’erreur binaire (BER) potentiel. Dans cette thèse, l’information de fading est déduite des simulations MR-FDPF et par la suite des valeurs réalistes de BER sont données. Enfin, ces données réalistes de BER permettent d’évaluer l’impact de schémas de modulation adaptatifs. Des résultats sont présentés dans trois configurations : systèmes SISO (mono-antenne à l’émission et à la réception), systèmes à diversité de type MRC, et systèmes large bande de type OFDM. / This thesis aims at proposing all the possible enhancements for the Multi-Resolution Frequency-Domain ParFlow (MR-FDPF) model. As a deterministic radio propagation model, the MR-FDPF model possesses the property of a high level of accuracy, but it also suffers from some common limitations of deterministic models. For instance, realistic radio channels are not deterministic but a kind of random processes due to, e.g. moving people or moving objects, thus they can not be completely described by a purely deterministic model. In this thesis, a semi-deterministic model is proposed based on the deterministic MR-FDPF model which introduces a stochastic part to take into account the randomness of realistic radio channels. The deterministic part of the semi-deterministic model is the mean path loss, and the stochastic part comes from the shadow fading and the small scale fading. Besides, many radio propagation simulators provide only the mean power predictions. However, only mean power is not enough to fully describe the behavior of radio channels. It has been shown that fading has also an important impact on the radio system performance. Thus, a fine radio propagation simulator should also be able to provide the fading information, and then an accurate Bit Error Rate (BER) prediction can be achieved. In this thesis, the fading information is extracted based on the MR-FDPF model and then a realistic BER is predicted. Finally, the realistic prediction of the BER allows the implementation of the adaptive modulation scheme. This has been done in the thesis for three systems, the Single-Input Single-Output (SISO) systems, the Maximum Ratio Combining (MRC) diversity systems and the wideband Orthogonal Frequency-Division Multiplexing (OFDM) systems.

La capacité à répondre aux changements environnementaux est cruciale pour l’établissement et la persistance des populations dans un système hétérogène. Les processus sous-jacents à cette capacité peuvent prendre différentes formes. La grande diversité génétique (et phénotypique) découlant de la reproduction sexuée est un des processus permettant à une population de répondre aux différentes conditions environnementales par la survie d’au moins quelques individus. D’autre part, les processus épigénétiques, en permettant la modification du patron d’expression des gènes, contribuent également à la variation phénotypique. Ces variations peuvent survenir accidentellement (épimutations) ou en réponse à un stimulus environnemental (plasticité). Les processus épigénétiques représenteraient ainsi une alternative à la variation génétique pouvant expliquer le succès écologique des organismes génétiquement identiques. Toutefois, les génotypes ne répondent pas tous de la même façon aux conditions environnementales ; certains génotypes sont considérés comme généralistes et peuvent s’acclimater à une vaste gamme de conditions environnementales alors que d’autres sont plutôt spécialistes et restreints à un type d’environnement donné. L’objectif général de cette thèse est de mettre en évidence certains des processus responsables de la persistance des organismes asexués en déterminant les relations entre la variation épigénétique, la variation phénotypique et les stratégies écologiques. Pour ce faire, des hybrides asexués Chrosomus eos-neogaeus, un poisson à reproduction clonale, ont servi de modèle biologique. Se reproduisant par gynogenèse, les lignées clonales (génotypes) doivent faire face aux mêmes variations environnementales que les espèces parentales sexuées. De plus, la répartition géographique de chacune des lignées suggère la présence de génotypes généralistes et spécialistes. L’analyse de ces lignées en milieux naturels et en milieux contrôlés a permis de décortiquer l’influence des variations génétique, environnementale et épigénétique sur la variation phénotypique. Dans un premier temps, les modèles de stratégies généraliste et spécialiste ont été testés de manière empirique : (i) des analyses génétiques ont permis d’inférer les processus historiques expliquant la diversité et la répartition actuelle des lignées clonales ; (ii) l’analyse du patron de ii méthylation de différentes lignées a permis de déterminer l’importance relative des sources de variations épigénétiques selon les fluctuations environnementales et de les associer à une stratégie écologique : une importante influence de l’environnement ou une plus grande stochasticité dans l’établissement des marques épigénétiques étant associées à la plasticité phénotypique ou au bet-hedging, respectivement ; et (iii) le rôle de la plasticité phénotypique dans la diversification de niches écologiques a été souligné par la comparaison de la variation de la morphologie trophique en milieux naturels et contrôlés. D’autre part, le second volet de cette thèse a permis d’associer un coût (détection d’une instabilité développementale) à la plasticité phénotypique et d’élaborer une hypothèse sur l’existence d’un handicap démographique nécessaire afin d’expliquer la situation contre-intuitive concernant la coexistence des organismes gynogènes et de leurs hôtes sexués. La compréhension des différents mécanismes sous-jacents au succès écologique des organismes face aux variations environnementales permet ainsi une meilleure évaluation de leur potentiel évolutif et fournit des outils supplémentaires pour leur protection face à un environnement changeant. / The capacity to cope with environmental changes is crucial to the establishment and persistence of populations. The processes underlying such a capacity can take different forms. The high genetic (and phenotypic) diversity arising from sexual reproduction is one process that allows to cope with different environmental conditions through the survival of at least a few individuals. On the other hand, epigenetic processes, allowing the modification of gene expression, are also responsible for phenotypic variation. Epigenetic changes may occur accidentally (epimutations) or in response to an environmental stimulus (plasticity). Thus, epigenetics would represent an alternative process to genetic variation to explain the ecological success of genetically identical organisms. However, genotypes are not equally capable of coping with environmental changes. Some genotypes are generalists and can acclimatize to a wide range of environmental conditions, whereas other genotypes are specialized and restricted to narrow environmental conditions. The general objective of this thesis is to highlight the processes responsible for the persistence of asexual organisms by determining the relationship between epigenetic processes, phenotypic variation and ecological strategies. To achieve this, the clonal hybrid fish Chrosomus eos-neogaeus were used as a biological model. By reproducing by gynogenesis, the clonal lineages (genotypes) are distributed among the same environments than the sexual parental species. Moreover, the geographical distribution of the lineages suggests the presence of generalist and specialist genotypes. The analysis of these lineages in natural and controlled conditions allowed to disentangling the influence of genetic, environmental and epigenetic variations on phenotypic variation. On the one hand, generalist and specialist strategies were empirically tested: (i) genetic analyses were used to infer the historical processes explaining the diversity and the current distribution of the clonal lineages; (ii) the comparison of methylation patterns in different lineages allowed to determine the dynamism of the epigenetic processes according to environmental fluctuations and to associate them with an ecological strategy: an important environmental or stochastic effect on epigenetic variation being associated with phenotypic iv plasticity or bet-hedging, respectively; and (iii) the role of phenotypic plasticity in niches diversification was highlighted by comparing individuals’ trophic morphology in natural and controlled conditions. On the other hand, the second part of this thesis has allowed to associate a cost (developmental instability) to phenotypic plasticity and to propose a hypothesis about the existence of a demographic handicap necessary to explain the paradox regarding the coexistence of sexual and asexual sperm-dependent organisms. Understanding these different mechanisms underlying the ecological success of organisms in face of environmental heterogeneity allows us to better establish their evolutionary potential and provides additional tools to protect them against changing environments.