L’étude présentée dans ce mémoire s’inscrit dans le cadre de la réutilisation des eaux usées traitées par un procédé d’oxydation avancée (AOP), la photocatalyse hétérogène. Ce procédé, couplant le rayonnement UV et l’utilisation d’un photocatalyseur (TiO2) au sein d’un réacteur, est envisagé comme procédé de traitement tertiaire pour la désinfection des effluents dis secondaires. Les expérimentations photocatalytiques ont été réalisées sur une bactérie cible, E.coli. Elles ont été conduites en mode batch puis en mode continu. Les expérimentations en mode batch ont été réalisées sous irradiation contrôlée puis solaire. Les données expérimentales acquises sous irradiation contrôlée ont permis la comparaison des performances bactéricides de différents catalyseurs. Elles ont conduit en parallèle à la définition d’un modèle cinétique représentatif de la capacité bactéricide de chaque média. Les expérimentations solaires ont permis de valider le modèle cinétique sous irradiation solaire puis, d’étudier l’inactivation bactérienne dans un effluent réel. Par ailleurs, le potentiel bactéricide du traitement photocatalytique en régime permanent a été évalué. Le fonctionnement du procédé continu a été parfaitement décrit par un modèle cinétique se basant sur la loi cinétique initialement définie en mode batch. Finalement, l’inactivation d’E.coli a été évaluée par différentes techniques de quantification bactérienne. Cela a permit de mettre en évidence le mécanisme principal d’inactivation par voie photocatalytique, la lyse membranaire et d’apporter des informations sur l’état de viabilité « réel » des bactéries au cours du traitement photocatalytique. / The study presented in this paper is part of the reuse of treated wastewater by advanced oxidation process (AOP), the heterogeneous photocatalysis. This process, coupling the UV radiation and the use of a photocatalyst (TiO2) in a reactor, is envisaged as tertiary treatment process for disinfection of said secondary effluent. Photocatalytic experiments were performed on a target bacterium, E. coli. They were conducted in batch and continuous mode. The experiments in batch mode were performed under controlled irradiation and sunlight. The experimental data obtained under controlled irradiation allowed the comparison of the bactericidal performance of different catalysts. They led in parallel to the definition of a representative kinetic model of the bactericidal capacity of each medium. Solar experiments were used to validate the kinetic model under solar irradiation and then to study the bacterial inactivation in a real effluent. Furthermore, the potential of the photocatalytic bactericidal treatment at steady state was evaluated. The operation of the continuous process has been thoroughly described by a kinetic model based on the kinetic law originally defined in batch mode. Finally, inactivation of E. coli was evaluated by different bacterial quantification techniques. This has made it possible to highlight the main mechanism of the photocatalytic bacterial inactivation, the membrane lysis. It provided information about the "real" state of the bacteria viability during the photocatalytic treatment.

Tesis por compendio / [ES] El acceso a fuentes de energía moderna en las áreas rurales de la región andina es uno de los factores principales para disminuir la pobreza ya que su acceso proporcionaría beneficios ambientales, económicos y sociales. Pese a los esfuerzos de buscar fuentes alternativas para subsanar el déficit energético, aún existen millones de personas que sufren la falta de accesibilidad a fuentes de energía moderna, situación que se debe a los altos niveles de pobreza bajo los cuales se encuentran inmersos. Junto a este inconveniente se suma el enorme incremento de residuos agrícolas en las comunidades andinas. Residuos que provienen de las actividades agrícolas, y que podrían ser perjudiciales para el medio ambiente si no se toman medidas adecuadas. Lamentablemente, en muchos países en desarrollo donde se generan grandes cantidades de estos residuos, se sabe poco sobre sus posibles riesgos y beneficios si no se gestionan adecuadamente. Uno de los enfoques más interesantes para abordar esta problemática, es el desarrollo de la gestión sostenible de los residuos orgánicos agrícolas de la región, transformándolos en recursos para la generación de energía renovable (biogás) y fertilizantes orgánicos (digestato). Esta solución permitiría dar una valorización energética a los residuos de la agricultura de la zona, sobre la cual basan su economía, y a la vez contribuiría a una mayor gestión de los residuos evitando el incremento de la contaminación ambiental. Con la finalidad de contribuir al desarrollo energético y mejorar el paradigma de la gestión de residuos en el área andina de Guaranda (Ecuador), la presente Tesis Doctoral aborda la evaluación del potencial bioquímico de metano (BMP) de los residuos orgánicos agrícolas de la región. Se realiza una cuantificación sistemática de la producción de biogás mediante la transformación bioquímica de residuos orgánicos agrícolas, que comprenden: sustratos principales (residuos de estiércol de vicuña, llama y cuy, y residuos de matadero de ganado vacuno) y cosustratos (residuos de paja de amaranto, quinua y trigo). El objetivo general de esta investigación de doctorado se ha llevado a cabo en cuatro fases: (I) Caracterización de la materia prima mediante el análisis elemental y proximal a través de los cuáles se estimó el rendimiento teórico y la biodegradabilidad de los sustratos y cosustratos, (II) Rendimiento de la codigestión de residuos orgánicos agrícolas con mezclas de lodos de aguas residuales en biodigestores batch, (III) Análisis de los efectos sinérgicos y antagónicos durante la monodigestión y codigestión de las materias primas y (IV) Evaluación de la cinética microbiana de la digestión anaerobia mediante los modelos de Gompertz modificado, transferencia, ecuación logística, modelo del cono y Richards modificado. En la caracterización fisicoquímica se determinó que las relaciones SV/ST de los sustratos y cosustratos oscilaron entre 58 y 77% con una relación C/N entre 12 y 102, lo que indicó que estos residuos son materias primas adecuadas para la producción de metano. En todos los ensayos un aumento de la cantidad de inóculo mejoró la biodegradabilidad de los sustratos y por consiguiente la producción metano; así, en la monodigestión se tuvo incrementos de hasta 90% y en la codigestión incrementos del 71%. Todas las mezclas produjeron efectos sinérgicos, donde los mayores porcentajes de metano se dieron cuando las mezclas de residuos de amaranto, quinua y trigo fueron del 50 y 75% de sólidos volátiles. Independientemente de la SIR1:1 y la SIR 1:2 se mejoró la producción de metano de la codigestión al incrementar el porcentaje de cosustrato especialmente de residuos de amaranto y quinua. Los mejores resultados de todos los ensayos realizados se obtuvieron en los biodigestores compuestos por residuos de matadero y residuos de quinua, donde se obtuvieron producciones de metano entre 581 y 555 ml / [CA] L'accés a fonts d'energia moderna en les àrees rurals de la regió andina és un dels factors principals per a disminuir la pobresa ja que el seu accés proporcionaria beneficis ambientals, econòmics i socials. Malgrat els esforços de buscar fonts alternatives per a esmenar el dèficit energètic, encara existeixen milions de persones que pateixen la falta d'accessibilitat a fonts d'energia moderna, situació que es deu als alts nivells de pobresa sota els quals es troben immersos. Al costat d'aquest inconvenient se suma l'enorme increment de residus agrícoles en les comunitats andines. Residus que provenen de les activitats agrícoles, i que podrien ser perjudicials per al medi ambient si no es prenen mesures adequades. Lamentablement, en molts països en desenvolupament on es generen grans quantitats d'aquests residus, se sap poc sobre els seus possibles riscos i beneficis si no es gestionen adequadament. Un dels enfocaments més interessants per a abordar aquesta problemàtica, és el desenvolupament de la gestió sostenible dels residus orgànics agrícoles de la regió, transformant-los en recursos per a la generació d'energia renovable (biogàs) i fertilitzants orgànics (digestato). Aquesta solució permetria donar una valorització energètica als residus de l'agricultura de la zona, sobre la qual basen la seua economia, i alhora contribuiria a una major gestió dels residus evitant l'increment de la contaminació ambiental. Amb la finalitat de contribuir al desenvolupament energètic i millorar el paradigma de la gestió de residus en l'àrea andina de Guaranda (l'Equador), la present Tesi Doctoral aborda l'avaluació del potencial bioquímic de metà (BMP) dels residus orgànics agrícoles de la regió. Es realitza una quantificació sistemàtica de la producció de biogàs mitjançant la transformació bioquímica de residus orgànics agrícoles que comprenen: substrats principals (residus de fem de vicunya, flama i cuy, i residus d'escorxador de bestiar boví), *cosustratos (residus de palla d'amarant, quinua i blat). L'objectiu general d'aquesta investigació de doctorat s'ha dut a terme en quatre fases: (I) caracterització de la matèria primera mitjançant l'anàlisi elemental i proximal a través dels quals es va estimar el rendiment teòric i la biodegradabilitat dels substrats i cosustratos, (II) Rendiment de la codigestión de residus orgànics agrícoles amb mescles de llots d'aigües residuals en biodigestores batch, (III) Anàlisis dels efectes sinèrgics i antagònics durant la monodigestión i codigestión de les matèries primeres i (IV) Avaluació de la cinètica microbiana de la digestió anaeròbia mitjançant els models de Gompertz modificat, transferència, equació logística, model del con i Richards modificat. En la caracterització fisicoquímica es va determinar que les relacions SV/ST dels substrats i cosustratos van oscil·lar entre 58 i 77% amb una relació C/N entre 12 i 102, la qual cosa va indicar que aquests residus són matèries primeres adequades per a la producció de metà. En tots els assajos un augment de la quantitat d'inòcul va millorar la biodegradabilitat dels substrats i per consegüent la producció metà; així, en la monodigestión es va tindre increments de fins a 90% i en la codigestión increments del 71%. Totes les mescles van produir efectes sinèrgics, on els majors percentatges de metà es van donar quan les mescles de residus d'amarant, quinua i blat van ser del 50 i 75% de sòlids volàtils. Independentment de la SIR1:1 i la SIR 1:2 es va millorar la producció de metà de la codigestión en incrementar el percentatge de cosustrato especialment de residus d'amarant i quinua. Els millors resultats de tots els assajos realitzats es van obtindre en els biodigestores compostos per residus d'escorxador i residus de quinua, on es van obtindre produccions de metà entre 581 i 555 ml/g VS. / [EN] Access to modern energy sources in rural areas of the Andean region is one of the main factors to reduce poverty, since its access would provide environmental, economic and social benefits. Despite efforts to find alternative sources to correct the energy deficit, there are still millions of people who suffer from the lack of accessibility to modern energy sources, a situation that is due to the high levels of poverty under which they are immersed. Along with this inconvenience is added the enormous increase in agricultural residues in the Andean communities. Waste that comes from agricultural activities, and that could be harmful to the environment if adequate measures are not taken. Unfortunately, in many developing countries where large amounts of these wastes are generated, little is known about their potential risks and benefits if not managed properly. One of the most interesting approaches to address this problem is the development of sustainable management of agricultural organic waste in the region, transforming it into resources for the generation of renewable energy (biogas) and organic fertilizers (digestate). This solution would allow to give an energetic recovery to the agricultural residues of the area, on which they base their economy, and at the same time would contribute to a better management of the residues avoiding the increase of environmental pollution. To contribute to energy development and improve the paradigm of waste management in the Andean area of Guaranda (Ecuador), this Doctoral Thesis addresses the evaluation of the biochemical potential of methane (BPM) of agricultural organic waste in the region. A systematic quantification of biogas production is carried out through the biochemical transformation of agricultural organic waste that includes main substrates (vicuña, llama and guinea pig manure residues, and cattle slaughterhouse residues) and co-substrates (amaranth straw residues), quinoa and wheat). The general objective of this doctoral research has been carried out in four phases: (I) characterization of the raw material through elemental and proximal analysis through which the theoretical performance and biodegradability of substrates and co-substrates were estimated, (II) Performance of the co-digestion of agricultural organic waste with mixtures of sewage sludge in batch biodigesters, (III) Analysis of synergistic and antagonistic effects during monodigestion and co-digestion of raw materials and (IV) Evaluation of microbial kinetics of anaerobic digestion using modified Gompertz models, transfer, logistic equation, cone model and modified Richards. In the physicochemical characterization it was determined that the VS/TS ratios of the substrates and co-substrates ranged between 58 and 77% with a C/N ratio between 12 and 102, which indicated that these wastes are suitable raw materials to produce methane. In all the tests an increase in the amount of inoculum improved the biodegradability of the substrates and consequently the methane production; thus, in monodigestion there were increases of up to 90% and in co-digestion increases of 71%. All the mixtures produced synergistic effects, where the highest percentages of methane occurred when the mixtures of amaranth, quinoa and wheat residues were 50 and 75% volatile solids. Regardless of SIR1:1 and SIR 1:2, the production of methane from co-digestion was improved by increasing the percentage of co-substrate, especially amaranth and quinoa residues. The best results of all the tests carried out were obtained in the biodigesters composed of slaughterhouse waste and quinoa waste, where methane productions between 581 and 555 ml/g VS were obtained. Regarding the kinetic modelling of the anaerobic digestion process, it was found that all the models fit the experimental values quite well with the predicted ones. In the monodigestion, in all the logistic models, the calculated asymptotes were adjusted very precisely for the specific yield (Me / This work has been carried out within the framework of the project “Analysis of the implementation of biomass exploitation chains in rural communities in the province of Bolívar (Ecuador)” of the ADSIEO-COOPERATION program of the Universitat Politècnica de València (UPV). The Ecuadorian Energy Exploitation Research Network of Biomass (ECUMASA) and the IBEROMASA Network (719RT0586) of the IberoAmerican Program of Science and Technology for Development (CYTED) have participated in this program / Meneses Quelal, WO. (2021). Optimization of Anaerobic Codigestion Processes of Lignocellulosic Materials of Difficult Degradation with Residues from Andean Livestock [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/171722 / Compendio

Les protéines fluorescentes, comme la GFP (green fluorescent protein), sont des protéines naturellement fluorescentes qui sont utilisées pour leur rôle de marqueur, permettant de localiser des protéines dans les cellules et d'en suivre les déplacements. De nombreuses études expérimentales et théoriques ont été menées ces dix dernières années sur les protéines fluorescentes. De là, se forge une compréhension essentiellement qualitative du rôle de la protéine vis-à-vis de l’obtention ou non d’une émission radiative : il apparaît que la protéine permet la fluorescence en bloquant les processus qui la désactivent ; ces processus de désactivation sont très rapides et efficaces (à l'échelle de la picoseconde) dans le cas du chromophore seul, et ils sont bien identifiés comme étant des torsions autour des liaisons intercycles (tau et phi). Dans la protéine, la sensibilité des temps de vie de fluorescence à des mutations proches ou non du chromophore, à des modifications de pH ou de température laisse supposer un contrôle de la dynamique du chromophore par différents paramètres, sans qu’ils soient pour autant identifiés et mis en relation.Une étude de la dynamique de la protéine permettrait de faire la lumière sur les mécanismes responsables de ces phénomènes photophysiques pour lesquels une analyse structurale ne suffit pas. Cependant l'étude de la dynamique est limitée par la taille du système (>30 000 atomes), par l'échelle de temps des phénomènes photophysiques considérés (dizaine de nanosecondes) et par le fait que les deux torsions tau et phi sont fortement couplées dans l'état excité du chromophore. Ces trois facteurs excluent les méthodes de dynamique existantes aujourd'hui ; dynamique quantique (AIMD), dynamique mixte classique-quantique (QM/MD) et dynamique moléculaire classique (MD).Nous avons surmonté le problème par la modélisation de la surface d’énergie potentielle de torsion du chromophore à l’état excité basée sur des calculs quantiques de haute précision, par une interpolation des valeurs obtenues par une expression analytique appropriée en fonction des angles de torsion tau et phi et avec une précision suffisante pour reproduire des barrières de l’ordre de la kcal/mol, et enfin, par l’implémentation de cette expression analytique dans le programme parallèle AMBER. Une deuxième difficulté théorique concerne la simulation et l’analyse statistique d’événements peu fréquents à l’échelle de la nanoseconde, et dont on ne connait pas le chemin de réaction, ici les déformations de la protéine et du chromophore conduisant aux géométries favorables à la conversion interne. Grâce à ces développements et aux simulations qu'ils ont permises, nous avons réalisé la première modélisation de la désactivation non-radiative par conversion interne à l’échelle de la nanoseconde dans trois protéines fluorescentes différentes. L’analyse des dynamiques moléculaires classiques nous donne une évaluation quantitative des temps de vie de l’extinction de fluorescence, en accord avec les données expérimentales. Par ailleurs elle nous a permis d'identifier les mouvements moléculaires concertés de la protéine et du chromophore conduisant à cette extinction. De ces résultats, émerge une représentation plus complète du mécanisme qui libère la torsion du chromophore ou qui la déclenche : il peut venir d’un mouvement spécifique de la protéine, qui se produit à l’échelle de la nanoseconde, ou bien de plusieurs mouvements spécifiques, plus fréquents (rupture de liaisons hydrogène, rotation de chaînes latérales, dynamique d'agrégats d’eau), mais qui coïncident seulement à l’échelle de la nanoseconde. Ces mouvements spécifiques n’ont pas un coût énergétique important mais la nécessité de leur coïncidence crée un délai de l’ordre de quelques nanosecondes alors que dans le vide la torsion se produit en quelques picosecondes. Dans le cas des protéines étudiées, on a identifié en grande partie les mécanismes et les acides aminés qui sont impliqués. / Fluorescent proteins, like GFP (green fluorescent protein), are efficient sensors for a variety of physical-chemical properties and they are extensively used as markers in living cells imaging. These proteins have been widely studied both experimentally and theoretically the last decade. The comprehension of the protein's role in the regulation of the radiative emission is today essentially qualitative: it appears that the protein enables the fluorescence by blocking the processes that deactivates it; the deactivating processes are very quick and efficient (on the picosecond time scale) when the chromophore is isolated, and they are identified as being the torsions around the central bonds of the chromophore (tau and phi). The fluorescence lifetimes of a protein is very sensitive to mutations in the vicinity of the chromophore, to modifications in pH or in temperature. This seems to indicate a control of the dynamics of the chromophore by different parameters, that are not necessarily identified.A study of the dynamics of the protein would allow a deeper understanding of the mechanisms that are responsible for the fluorescence quenching. From a theoretical point of view, one is faced with three difficulties in this type of study: the size of the system (>30 000 atoms including a water box), the required time scale (tens of nanoseconds) and the fact that the torsions tau and phi are strongly coupled in the excited state of the chromophore. We must thus rule out the already existing dynamics methods: quantum dynamics (AIMD), mixed classical-quantum dynamics (QM/MD) and classical molecular dynamics (MD).We have overcome this problem by modeling the torsional potential energy surface of the chromophore in the first excited state trough high precision quantum calculations, by interpolating the energy values with an analytical fitting expression depending on the torsions tau and phi and with a precision high enough to reproduce barriers of the order of 1 kcal/mol, and lastly, by implementing this fitting expression in a parallelized version of the MD program AMBER. Another theoretical difficulty concerns the simulation and the statistical analysis of rare events on the nanosecond time scale without knowing the reaction path in advance, i.e. the deformations of the protein and of the chromophore leading to geometries where the internal conversion is favored. As a result of these developments and of the simulations they have enabled, we have been able to model, for the first time, the non-radiative deactivation by internal conversion at the nanosecond time scale in three different fluorescent proteins. The analysis of the classical molecular dynamics gives us a quantitative evaluation of the lifetime of the fluorescence extinction, in agreement with experimental results. In addition, it has allowed us to identify the concerted molecular movements between the protein and the chromophore leading to this extinction. A more complete representation of the mechanism that liberates or provokes the chromophore torsion emerges from these results: it could be a specific movement of the protein, that occurs on the nanosecond timescale, or several specific movements that occur more frequently (breakage of a hydrogen bond, rotation of side chains, dynamics of a water cluster), but that coincide only on the nanosecond time scale. These specific movements do not have a high energy cost but the need for them to coincide creates a delay of several nanoseconds compared to the chromophore torsion in vacuo which occurs after a few picoseconds. In the proteins we have studied (GFP, YFP and Padron), we have identified the principle components of the mechanisms and the amino acids that are implicated in this chromophore-protein interplay.

This thesis, which contains fourteen chapters in two parts, presents theoretical and computer simulation studies of dynamics in supercooled liquids and thermotropic liquid crystals. These two apparently diverse physical systems are unified by a startling similarity in their complex slow dynamics. Part I consists of six chapters on supercooled liquids while Part II comprises seven chapters on thermotropic liquid crystals. The fourteenth chapter provides a concluding note. Part I starts with an introduction to supercooled liquids given in chapter 1. This chapter discusses basic features of supercooled liquids and the glass transition and portrays some of the theoretical frameworks and formalisms that are widely recognized to have contributed to our present understanding. Chapter 2 introduces a new model of binary mixture in order to study dynamics across the supercooled regime. The system consists of an equimolar mixture of the Lennard-Jones spheres and the Gay-Berne ellipsoids of revolution, and thus one of its components has orientational degrees of freedom (ODOF). A decoupling between trans-lational diffusion and rotational diffusion is found to occur below a temperature where the second rank orientational correlation time starts showing a steady deviation from the Arrhenius temperature behavior. At low temperatures, the optical Kerr effect (OKE) signal derived from the system shows a short-to-intermediate time power law decay with a very weak dependence on temperature, if at all, of the power law exponent as has been observed experimentally. At the lowest temperature investigated, jump motion is found to occur in both the translational and orientational degrees of freedom. Chapter 3 studies how the binary mixture, introduced in the previous chapter, explores its underlying potential energy landscape. The study reveals correlations between the decoupling phenomena, observed almost universally in supercooled molecular liquids, and the manner of exploration of the energy landscape of the system. A significant deviation from the Debye model of rotational diffusion in the dynamics of ODOF is found to begin at a temperature at which the average inherent structure energy of the system starts falling as the temperature decreases. Further, the coupling between rotational diffusion and translational diffusion breaks down at a still lower temperature, where a change occurs in the temperature dependence of the average inherent structure energy. Chapters 4-6 describe analytical and numerical approaches to solve kinetic models of glassy dynamics for various observables. The β process is modeled as a thermally activated event in a two-level system and the a process is described as a β relaxation mediated cooperative transition in a double-well. The model resembles a landscape picture, conceived by Stillinger [Science 267, 1935 (1995)], where the a process is assumed to involve a concerted series of the β processes, the latter being identified as elementary relaxations involving transitions between contiguous basins. For suitable choice of parameter values, the model could reproduce many of the experimentally observed features of anomalous heat capacity behavior during a temperature cycle through the glass transition as described in chapter 4. The overshoot of the heat capacity during the heating scan that marks the glass transition is found to be caused by a delayed energy relaxation. Chapter 5 shows that the model can also predict a frequency dependent heat capacity that reflects the two-step relaxation behavior. The high-frequency peak in the heat capacity spectra appears with considerably larger amplitude than the low-frequency peak, the latter being due to the a relaxation. The model, when simplified with a modified description of the a process that involves an irreversible escape from a metabasin, can be solved analytically for the relaxation time. This version of the model captures salient features of the structural relaxation in glassy systems as described in chapter 6. In Part II, thermotropic liquid crystals are studied in molecular dynamics simulations using primarily the family of the Gay-Berne model systems. To start with, chapter 7 provides a brief introduction to thermotropic liquid crystals, especially from the perspective of the issues discussed in the following chapters. This chapter ends up with a detail description of the family of the Gay-Berne models. Chapter 8 demonstrates that a model system for calamitic liquid crystal (comprising rod-like molecules) could capture the short-to-intermediate time power law decay in the OKE signal near the isotropic-nematic (I-N) phase transition as observed experimentally. The single-particle second rank orientational time correlation function (OTCF) for the model liquid crystalline system is also found to sustain a power law decay regime in the isotropic phase near the I-N transition. On transit across the I-N phase boundary, two power law decay regimes, separated by a plateau, emerge giving rise to a step-like feature in the single-particle second rank OTCF. When the time evolution of the rotational non-Gaussian parameter is monitored as a diagnostic of spatially heterogeneous dynamics, a dominant peak is found to appear following a shoulder at short times, signaling the growth of pseudonematic domains. These observations are compared with those relevant ones obtained for the supercooled binary mixture, as discussed in chapter 2, in the spirit of the analogy suggested recently by Fayer and coworkers [J. Chem. Phys. 118, 9303 (2003)]. In chapter 9, orientational dynamics across the I-N transition are investigated in a variety of model systems of thermotropic liquid crystals. A model discotic system that consists of disc-like molecules as well as a lattice system have been considered in the quest of a universal short-to-intermediate time power law decay in orientational relaxation, if any. A surprisingly general power law decay at short to intermediate times in orientational relaxation is observed in all these systems. While the power law decay of the OKE signal has been recently observed experimentally in calamitic systems near the I-N phase boundary and in the nematic phase by Fayer and coworkers [J. Chem. Phys. 116, 6339 (2002), J. Phys. Chem. B 109, 6514 (2005)], the prediction for the discotic system can be tested in experiments. Chapter 10 presents the energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals by determining the inherent structures of a family of one-component Gay-Berne model systems. This study throws light on the interplay between the orientational order and the translational order in the mesophases the systems exhibit. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures. The inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the I-N transition and this breakdown is found to occur at a temperature below which the system explores increasingly deeper potential energy minima. There exists a remarkable similarity in the manner of exploration of the potential energy landscape between the Gay-Berne systems studied here and the well known Kob-Andersen binary mixture reported previously [Nature, 393, 554 (1998)]. In search of a dynamical signature of the coupling between orientational order and translational order, anisotropic translational diffusion in the nematic phase has been investigated in the Gay-Berne model systems as described in chapter 11. The translational diffusion coefficient parallel to the director D// is found to first increase and then decrease as the temperature drops through the nematic phase. This reversal occurs where the smectic order parameter of the underlying inherent structures becomes significant for the first time. The non-monotonic temperature behavior of D// can thus be viewed from an energy landscape analysis as a dynamical signature of the coupling between orientational and translational order at the microscopic level. Such a view is likely to form the foundation of a theoretical framework to explain the anisotropic translation diffusion. Chapter 12 investigates the validity of the Debye model of rotational diffusion near the I-N phase boundary with a molecular dynamics simulation study of a Gay-Berne model system for calamitic liquid crystals. The Debye model is found to break down near the I-N phase transition. The breakdown, unlike the one observed in supercooled molecular liquids where a jump diffusion model is often invoked, is attributed to the growth of orientational pair correlation. A mode-coupling theory analysis is provided in support of the explanation. Chapter 13 presents a molecular dynamics study of a binary mixture of prolate ellipsoids of revolution with different aspect ratios interacting with each other through a generalized Gay-Berne potential. Such a study allows to investigate directly the aspect ratio dependence of the dynamical behavior. In the concluding note, chapter 14 starts with a brief summary of the outcome of the thesis and ends up with suggestion of a few relevant problems that may prove worthwhile to be addressed in future.

Die als Absorbermaterial für Dünnschichtsolarzellen geeigneten Verbindungshalbleiter Cu2ZnSnS4 (CZTS) und Cu2ZnSnS(4-x)Sex (x<3, CZTSSe) konnten erfolgreich durch Kombination der elektrochemischen Legierungsabscheidung und der anschließenden Sulfurisierung in H2S-haltiger Atmosphäre hergestellt werden. In früheren Arbeiten wurden die viel versprechenden Eigenschaften von CZTS und Cu2ZnSnSe4 (CZTSe), als In und Ga freie und damit kostengünstige Alternativen, bereits ausführlich vorgestellt. Im Rahmen dieser Arbeit konnte anhand von kristallographischen Ergebnissen sowie durch Untersuchungen der Bandlückenenergien bestätigt werden, dass die Kesterite CZTS (1,46eV) und CZTSSe (1,32eV) erfolgreich mittels einer nasschemischen Vorstufe herstellbar sind. Weiterhin wurde erstmalig der Zusammenhang unterschiedlicher Stöchiometrien anhand ermittelter Halbleitereigenschaften (Na, Eg, EFB) gezeigt. Auf diesen Ergebnissen basierend wurde eine optimale Zusammensetzung zur Herstellung funktionaler Absorberschichten bestimmt. Dennoch zeigt sich, dass die Prozessparameter der Gasphasen-Sulfurisierung entscheidend die Bildung homogener Schichten beeinflusst. Die beobachtete große Kristallverteilung und die dabei auftretenden lokalen Löcher setzten die Funktionalität der hergestellten Solar Zellen (Al/ZnO:Al/CdS/CZTS/Mo/Glas) deutlich herab. Trotz der geringen Wirkungsgrade konnte aus einer Reihe unterschiedlicher Absorbermaterialien eine optimale Stöchiometrie (~Cu2Zn1.1Sn0.9S4) ermittelt werden. Die elektrochemische Coabscheidung von Se (~Cu2Zn1.2Sn0.9Se0.3) und die dadurch erfolgte partielle Substitution von S durch Se bewirkte, verglichen zur CZTS Morphologie, eine kompaktere und geschlossene Schichtstruktur. Der Einfluss des Selenanteils wurde dabei anhand detaillierter kristallographischer Untersuchungen und einer reduzierten Bandlückenenergie (1,32eV) bestätigt. Obwohl deutlich reproduzierbare Diodeneigenschaften über große Flächen beobachtet wurden, konnten keine Verbesserung des Wirkungsgrads erzielt werden. Cu2ZnSn (CZT) und Cu2ZnSnSe0.3 (CZTSe) Precursorschichten wurden mittels eines neu entwickelten alkalischen sowie zyanidfreien Elektrolyten auf Mo beschichteten Glassubstraten abgeschieden. Dieser alkalische Elektrolyt zeigte eine hohe Langzeitstabilität und die bisher unbekannte Möglichkeit der Abscheidung hoher Zinnanteile bei niedrigen Temperaturen. Aufgrund detaillierter elektrochemischer Untersuchungen konnte ein fundamentales Verständnis hinsichtlich der Einflüsse unterschiedlicher Additive, Konzentrationen und Temperaturen erzielt werden. Diese Ergebnisse konnten zur Interpretation der beobachteten potentialabhängigen Legierungsbildung herangezogen werden. Im Rahmen eines wesentlich fundamentalen Ansatzes erfolgte weiterhin die Charakterisierung der Legierungsbildung, ausgehend von unterschiedlicher Metallgehalte im Elektrolyten, anhand eines kürzlich publizierten kinetischen Modells zur elektrochemischen Legierungsabscheidung. Basierend auf diesen Untersuchungen konnte das vorgestellte Badsystem aufgrund einer genauen Einstellbarkeit und Nachdosierung erfolgreich zur ternären Abscheidung von Precursorschichten verwendet werden. / Cu2ZnSnS4 (CZTS) and Cu2ZnSnS(4-x)Sex (x<0.3, CZTSSe) thin film solar cell absorber materials were successfully formed by combining a one step electrochemical precursor deposition followed by a vapour phase sulfurization process. CZTS and Cu2ZnSnSe4 (CZTSe) are known as promising candidates for thin film solar cell applications without using rare and thus expensive materials like In and Ga. This thesis confirmed by XRD and band gap energy data the potential to produce the kesterite type semiconductor materials CZTS (1,46eV) and CZTSSe (1,32eV) via a wet chemical precursor step. This paper presents for the first time the impact of different absorber compositions on semiconductor properties (NA, Eg, EFB) of the bulk material. Based on this data an optimum stoichiometry was identified to produce a functional absorber layer. However, sulfurization remained as the most critical process to achieve homogeneous thin films. In the most cases local pin holes and a large crystal size distribution diminished the conversion efficiency of produced solar cell samples (Al/ZnO:Al/CdS/CZTS/Mo/glass). Nevertheless an optimum performance was found for a slight excess of Zn (~Cu2Zn1.1Sn0.9S4). The electrochemical codeposition of Se (~Cu2Zn1.2Sn0.9Se0.3) at the precursor step enabled to do a partial substitution of S by Se which was identified to improve CZTS morphology into a homogeneous and dense layer. The expected impact of Se was also confirmed by detailed crystallographic and band gap energy (1.32eV) measurements. Although solar cell function was found for enlarged areas the low overall conversion efficiency could be not pushed to higher levels. Cu2ZnSn (CZT) and Cu2ZnSnSe0.3 (CZTSe) precursor layers were directly electrodeposited on Mo coated soda line glass substrates from a new developed alkaline cyanide free alloy bath system. The presented electrolyte showed high long term stability and an up to now unknown high rate of Sn codeposition at low electrolyte temperatures. Results of a detailed electrolyte characterization gave a fundamental understanding of additive, concentration and temperature effects. This knowledge was successfully linked to explain the potential depended alloy composition effects. As a more fundamental approach a new kinetic model of the electrochemical alloy deposition was used to characterize the impact of changed electrolyte metal contents on the resulting alloy composition. Based on this data the presented alloy bath system was successfully applied for precise adjustment and replenishment during the ternary precursor deposition.

Beaucoup de méthodes numériques ont été développées pour résoudre l'équation de Vlasov, car obtenir des simulations numériques précises en un temps raisonnable pour cette équation est un véritable défi. Cette équation décrit en effet l'évolution de la fonction de distribution de particules (électrons/ions) qui dépend de 3 variables d'espace, 3 variables de vitesse et du temps. L'idée principale de cette thèse est de réécrire l'équation de Vlasov sous forme d'un système hyperbolique par semi-discrétisation en vitesse. Cette semi-discrétisation est effectuée par méthode d'éléments finis. Le modèle ainsi obtenu est appelé équation de Vlasov réduite. Nous proposons différentes méthodes numériques pour résoudre efficacement ce modèle: méthodes des volumes finis, méthodes semi-Lagrangiennes et méthodes Galerkin discontinus. / Many numerical methods have been developed in order to selve the Vlasov equation, because computing precise simulations in a reasonable time is a real challenge. This equation describes the time evolution of the distribution function of charged particles (electrons/ions), which depends on 3 variables in space, 3 in velocity and time. The main idea of this thesis is to rewrite the Vlasov equation in the form of a hyperbolic system using a semi-discretization of the velocity. This semi-discretization is achieved using the finite element method. The resulting model is called the reduced Vlasov equation. We propose different numerical methods to salve this new model efficiently: finite volume methods, semi-Lagrangian methods and discontinuous Galerkin methods.

Les procédés de gazéification de bois à lits fixes étagés sont adaptés à la production d'électricité de petites puissances. Dans ces procédés, la pyrolyse est opérée dans un réacteur continu à lit fixe descendant. La particularité de ce type de réacteur est son fonctionnement autothermique. L'énergie nécessaire au chauffage, au séchage et à la pyrolyse est apportée par la combustion partielle du bois : on parle de “pyrolyse oxydante”. L'injection d'air par le haut du réacteur provoque la propagation d'une zone d'oxydation dans le milieu poreux à contre-courant des écoulements des solides et des gaz. Les travaux présentés dans ce manuscrit visent une meilleure description de cette étape du procédé. Le problème posé est de type multi-échelles. Ainsi, nous avons préalablement mené une étude à l'échelle de la particule isolée avant de s'intéresser au comportement global du lit fixe. A l'échelle de la particule, nous avons quantifié l'effet de l'oxygène et de la taille des particules sur la cinétique de la pyrolyse oxydante. Cette étude nous a guidés pour la mise en place d'un modèle cinétique de cette transformation. A l'échelle du lit fixe, la propagation de la zone d'oxydation a été caractérisée par des approches expérimentale et numérique, offrant ainsi une meilleure connaissance de cette étape du procédé étagé. / Wood Multi-staged gasification in a fixed bed reactor is suitable for small-scale electricity generation. In these processes, the pyrolysis is performed in a continuous downward fixed bed reactor. The main feature of this reactor is the autothermal operation. Energy for heating, drying and pyrolysis is supplied by partial combustion of wood, known as “oxidative pyrolysis”. The air introduced from the top of the reactor induces a combustion front that propagates countercurrent with the solids and gazes flows. The work presented in this document aimed to achieve a better description of this process. A multi-scale approach was considered. Therefore, we have firstly studied the behavior of an isolated particle before focusing on the overall fixed bed. At the particle scale, we have quantified the effect of oxygen and of particle size on the oxidative pyrolysis kinetics. This led us to the setup of a kinetic model for this transformation.At the fixed bed scale, the propagation of the combustion front was studied considering the experimental and numerical approaches, which provides a better understanding of this step of the wood staged gasifiers.

Les écoulements diphasiques jouent un rôle prépondérant dans les moteurs-fusées à ergols liquides cryogéniques, équipant par exemple les lanceurs de la famille Ariane. L'étude expérimentale de tels engins propulsifs étant complexe et onéreuse, disposer d'outils numériques à même de simuler fidèlement leur fonctionnement se révèle être un objectif aussi important qu'ambitieux. La difficulté majeure réside dans le caractère fortement multi-échelles du problème, si bien qu’aucune approche numérique existante n'est capable à elle seule de décrire parfaitement l'ensemble des échelles liquides. Partant de ce constat, les travaux présentés dans cette thèse visent à mettre en place une stratégie de couplage entre des modèles bien adaptés aux différentes topologies d'écoulement diphasique, et ce dans le cadre de la plateforme logicielle multi-physique CEDRE développée par l'ONERA. La démarche adoptée consiste précisément à coupler un modèle à interface diffuse de type ``4 équations'' pour les zones à phases séparées, et un modèle cinétique eulérien pour la phase dispersée, rendant ainsi possible la description de l’atomisation primaire. Par ailleurs, les conditions sévères qui règnent dans les moteurs cryotechniques, où de forts gradients de température, vitesse et densité sont rencontrés, mettent à l'épreuve la robustesse des méthodes numériques. Une nouvelle méthode MUSCL multipente pour maillages non structurés généraux a ainsi été développée, permettant d’améliorer la robustesse et la précision des schémas de discrétisation spatiale. L’ensemble de la stratégie de couplage est finalement appliquée à la simulation du banc Mascotte de l'ONERA pour la combustion cryotechnique. / Two-phase flows play a significant role for the proper functioning of cryogenic liquid-propellant rocketengines, such as those that equip the launchers of the Ariane family. Since the experimental investigationof such propulsion devices is complex and expensive, developing numerical tools able to accuratelysimulate their functioning, is a crucial but nonetheless ambitious objective. The major difficulty is due tothe multiscale nature of the problem, as a result of which there is currently no numerical approach ableto perfectly describe all the liquid scales on its own. Based on this observation the work presented in thisthesis aims at setting up a coupling strategy between models well-adapted to each two-phase flowtopology, in the framework of the ONERA’s multiphysics CEDRE software. The approach adoptedprecisely consists in coupling a 4-equation diffuse interface model for the separated phases and aeulerian kinetic model for the dispersed phase, thus making it possible to describe primary atomization.Besides, the harsh conditions within cryogenic rocket engines, where large temperature, velocity anddensity gradients are encountered, severely challenge the robustness of numerical methods. A newmultislope MUSCL method for general unstructured meshes is thus developed in order to improve therobustness and accuracy of space discretization schemes. The whole coupling strategy is finally appliedto the numerical simulation of the ONERA’s Mascotte test bench for cryogenic combustion research.

In many countries over the world (including Sweden), metal toxicity in freshwater resources causes a severe drinking water quality problem and poses a threat to the environment and human health. Among the different toxic metals in the water resources of Sweden, arsenic and uranium are the biggest threats to health. These elements, over long time consumption, may even lead to cancer and/or neurological disorder. Most of the wells are installed in crystalline and sedimentary bedrock and the received water comes from water bearing fractures in the bedrock. The handling of such water is an issue and there is a need to reduce the arsenic and uranium exposure by improving processes and technologies. It is a very serious problem demanding a safe, sustainable and eco-friendly arsenic and uranium removal technology prior to drinking water supply. Different treatment systems are available, but many of them are not suitable due to their high cost, operation complexity and waste management issues. Through this study, chitosan biopolymer the second largest abundant polysaccharide on earth after cellulose, was verified as a potential adsorbent for arsenic(V) and uranium(VI) removal from water solution. Adsorbent characterizations were also conducted by XRD, FTIR, SEM, UV-visible spectrum and TGA/DTA investigations. Bench-scale batch experiments were conducted using chitosan biopolymer (DDA-85%) as an adsorbent to determine the arsenic(V) and uranium(VI) removal efficiency, by allowing four important effective parameters e.g. chitosan dosages, pH, contact time and contaminant concentration. The adsorption data at optimum conditions were fitted with Langmuir, Freundlich and Dubinin-Radushkhevic (D-R) isotherm and Lagergren pseudo-first-order and pseudo-second-order kinetic model to investigate the adsorption process. The characterization of materials assured the presence of effective amino, hydroxyl, and carboxyl groups of chitosan. Another advanntage is that the materials are bio-degradable. The results show that the arsenic(V) and uranium(VI) removal efficiency was 100% and 97.45% after 300 minutes with optimum pH of 6.0 and 7.0 respectively. The optimum adsorbent dosages and initial concentration were 60 and 80g/L and 100 and 250 µg/L respectively. The adsorption process was suitably described by Freundlich isotherm (R2 = 0.9933) and Langmuir isotherm (R2 = 0.9858) correspondingly for arsenic(V) uranium(VI) compared to other isotherms. This is an important indicator of homogeneous monolayer adsorption of metals. For both of arsenic(V) and uranium(VI), pseudo-second-order explained the adsorption kinetics better than pseudo-first-order and the second-order kinetic regression coefficient (R2) were 0.9959 and 0.9672 correspondingly. Connecting to the above mentioned results, it can be summed up that the chitosan biopolymer (DDA 85%) can be used as an inexpensive, sustainable and environment-friendly treatment option for arsenic(V) and uranium(VI) contaminated drinking water. / I många länder världen runt (även i Sverige) orsakar metallers toxicitet besvärliga vattenkvalitetsproblem och utgör ett hot mot människors hälsa. Bland de toxiska metaller som finns i svenska vatten utgör arsenik och uran i dricksvatten allvarliga hälsorisker vid långvarig exposition då de kan orsaka cancer och neurologiska problem. Flertalet brunnar är installerade i kristallint berg och sedimentära bergarter och vattnet kommer vanligen från sprickor i berggrunden. Hanteringen av sådant vatten kan kräva reduktion av expositionen för arsenik- och uraninnehåll genom förbättrade processer och teknologier. Detta är ett angeläget problem som kräver en säker, pålitlig och ekovänlig teknologi att tillämpas innan vattnet distribueras. En rad olika behandlingssystem är tillgängliga men många av dem är inte lämpliga beroende på deras höga kostnad, den komplicerade tillämpningen och problem med hanteringen av restprodukter. I denna studie has biopolymeren chitosan, den näst vanligaste polymeren efter cellulosa, konstaterats vara en möjlig adsorbent för att avlägsna arsenik(V) och uran(VI) från vatten. Karakterisering av adsorbenten har också genomförts genom XRD, FTIR, SEM, UV och strålning i synligt ljus samt TGA/DTA undersökningar. Batch-tester i bänkskala har genomförts med användning av chitosan (DDA-85%) som adsorbent för att bestämma dess förmåga att avlägsna arsenik(V) och uran(VI)genom att variera fyra parametrar, nämligen kontakttid, pH, dos av chitosan och halt av föroreningen. Adsorptionsdata vid optimala förhållanden bestämdes genom tillämpning av Langmuir, Freundlich och Dubinin-Radushkhevic (D-R) isotermerna. Vidare tillämpades Lagergrens pseudo-first-order och pseudo-second-order kinetiska modell för att undersöka adsorptionsprocessen. Karakteriseringen av materialet visade förefintligheten av effektiva amino- (N-H), hydroxyl- (O-H) samt karboxylgrupper (C=O) i chitosan-polysackariden och att det är lätt nedbrytbart. Preliminära resultat visar att reduktionen av arsenik(V) och uran(VI) var 100 respektive 97,45 % efter 300 minuters kontakttid med optimalt pH på 6,0 respektive 7,0. De optimala doserna av adsorbent och den initiala koncentrationen var 60 och 80 g/L och 100 och 250 µg/L. Adsorptions process beskrevs bäst av Freundlich-isotermen för arsenik(V) (R2 = 0.9933) och med Langmuir-isotermen för uran(VI) (R2 = 0,9858) jämfört med andra isotermer vilket var en viktig indikation på en homogen monolager-adsorption. För både arsenik(V) och uran(VI) beskrev pseudo-second order adsorptionen bättre än pseudo-first-order. Second-order kinetiska regressionskoefficienten (R2) var 0.9959 och 0.9872 respektive. De ovanstående resultaten visar sammanfattningsvis att chitosan (DDA-85%) kan användas som en billig, pålitlig och miljövänlig behandlingsmetod av vatten för arsenik(V) och uran(VI). / <p>QC 20150526</p> / ChitoClean

Die als Absorbermaterial für Dünnschichtsolarzellen geeigneten Verbindungshalbleiter Cu2ZnSnS4 (CZTS) und Cu2ZnSnS(4-x)Sex (x&amp;lt;3, CZTSSe) konnten erfolgreich durch Kombination der elektrochemischen Legierungsabscheidung und der anschließenden Sulfurisierung in H2S-haltiger Atmosphäre hergestellt werden. In früheren Arbeiten wurden die viel versprechenden Eigenschaften von CZTS und Cu2ZnSnSe4 (CZTSe), als In und Ga freie und damit kostengünstige Alternativen, bereits ausführlich vorgestellt. Im Rahmen dieser Arbeit konnte anhand von kristallographischen Ergebnissen sowie durch Untersuchungen der Bandlückenenergien bestätigt werden, dass die Kesterite CZTS (1,46eV) und CZTSSe (1,32eV) erfolgreich mittels einer nasschemischen Vorstufe herstellbar sind. Weiterhin wurde erstmalig der Zusammenhang unterschiedlicher Stöchiometrien anhand ermittelter Halbleitereigenschaften (Na, Eg, EFB) gezeigt. Auf diesen Ergebnissen basierend wurde eine optimale Zusammensetzung zur Herstellung funktionaler Absorberschichten bestimmt. Dennoch zeigt sich, dass die Prozessparameter der Gasphasen-Sulfurisierung entscheidend die Bildung homogener Schichten beeinflusst. Die beobachtete große Kristallverteilung und die dabei auftretenden lokalen Löcher setzten die Funktionalität der hergestellten Solar Zellen (Al/ZnO:Al/CdS/CZTS/Mo/Glas) deutlich herab. Trotz der geringen Wirkungsgrade konnte aus einer Reihe unterschiedlicher Absorbermaterialien eine optimale Stöchiometrie (~Cu2Zn1.1Sn0.9S4) ermittelt werden. Die elektrochemische Coabscheidung von Se (~Cu2Zn1.2Sn0.9Se0.3) und die dadurch erfolgte partielle Substitution von S durch Se bewirkte, verglichen zur CZTS Morphologie, eine kompaktere und geschlossene Schichtstruktur. Der Einfluss des Selenanteils wurde dabei anhand detaillierter kristallographischer Untersuchungen und einer reduzierten Bandlückenenergie (1,32eV) bestätigt. Obwohl deutlich reproduzierbare Diodeneigenschaften über große Flächen beobachtet wurden, konnten keine Verbesserung des Wirkungsgrads erzielt werden. Cu2ZnSn (CZT) und Cu2ZnSnSe0.3 (CZTSe) Precursorschichten wurden mittels eines neu entwickelten alkalischen sowie zyanidfreien Elektrolyten auf Mo beschichteten Glassubstraten abgeschieden. Dieser alkalische Elektrolyt zeigte eine hohe Langzeitstabilität und die bisher unbekannte Möglichkeit der Abscheidung hoher Zinnanteile bei niedrigen Temperaturen. Aufgrund detaillierter elektrochemischer Untersuchungen konnte ein fundamentales Verständnis hinsichtlich der Einflüsse unterschiedlicher Additive, Konzentrationen und Temperaturen erzielt werden. Diese Ergebnisse konnten zur Interpretation der beobachteten potentialabhängigen Legierungsbildung herangezogen werden. Im Rahmen eines wesentlich fundamentalen Ansatzes erfolgte weiterhin die Charakterisierung der Legierungsbildung, ausgehend von unterschiedlicher Metallgehalte im Elektrolyten, anhand eines kürzlich publizierten kinetischen Modells zur elektrochemischen Legierungsabscheidung. Basierend auf diesen Untersuchungen konnte das vorgestellte Badsystem aufgrund einer genauen Einstellbarkeit und Nachdosierung erfolgreich zur ternären Abscheidung von Precursorschichten verwendet werden. / Cu2ZnSnS4 (CZTS) and Cu2ZnSnS(4-x)Sex (x&amp;lt;0.3, CZTSSe) thin film solar cell absorber materials were successfully formed by combining a one step electrochemical precursor deposition followed by a vapour phase sulfurization process. CZTS and Cu2ZnSnSe4 (CZTSe) are known as promising candidates for thin film solar cell applications without using rare and thus expensive materials like In and Ga. This thesis confirmed by XRD and band gap energy data the potential to produce the kesterite type semiconductor materials CZTS (1,46eV) and CZTSSe (1,32eV) via a wet chemical precursor step. This paper presents for the first time the impact of different absorber compositions on semiconductor properties (NA, Eg, EFB) of the bulk material. Based on this data an optimum stoichiometry was identified to produce a functional absorber layer. However, sulfurization remained as the most critical process to achieve homogeneous thin films. In the most cases local pin holes and a large crystal size distribution diminished the conversion efficiency of produced solar cell samples (Al/ZnO:Al/CdS/CZTS/Mo/glass). Nevertheless an optimum performance was found for a slight excess of Zn (~Cu2Zn1.1Sn0.9S4). The electrochemical codeposition of Se (~Cu2Zn1.2Sn0.9Se0.3) at the precursor step enabled to do a partial substitution of S by Se which was identified to improve CZTS morphology into a homogeneous and dense layer. The expected impact of Se was also confirmed by detailed crystallographic and band gap energy (1.32eV) measurements. Although solar cell function was found for enlarged areas the low overall conversion efficiency could be not pushed to higher levels. Cu2ZnSn (CZT) and Cu2ZnSnSe0.3 (CZTSe) precursor layers were directly electrodeposited on Mo coated soda line glass substrates from a new developed alkaline cyanide free alloy bath system. The presented electrolyte showed high long term stability and an up to now unknown high rate of Sn codeposition at low electrolyte temperatures. Results of a detailed electrolyte characterization gave a fundamental understanding of additive, concentration and temperature effects. This knowledge was successfully linked to explain the potential depended alloy composition effects. As a more fundamental approach a new kinetic model of the electrochemical alloy deposition was used to characterize the impact of changed electrolyte metal contents on the resulting alloy composition. Based on this data the presented alloy bath system was successfully applied for precise adjustment and replenishment during the ternary precursor deposition.