A systematic study of the crystallization of terthiophene, chosen as a model compound, has been carried out using the thermal gradient technique. We have observed that nucleation and growth can be decoupled for organic semiconductors (OSC) crystallizing from the melt in a temperature gradient and that these conditions lead to the generation of highly textured thin films with uniaxial in-plane alignment. Furthermore, adequate gradient conditions allow the selective growth of a single polymorphic form of terthiophene. The last results obtained on terthiophene concern the orientation of the unit cell with the reciprocal vector c* normal to the substrate and the alignment of the [100] and [-100] directions parallel to the gradient direction. It is hypothesized that the geometry of the system and the temperature profile induce a preferential fast growth direction perpendicular to the gradient direction.<p>In order to validate these results, we embarked on an exploratory study of the crystallization of a set of organic semiconductors, carefully selected based on rational arguments, to evaluate the potential of the thermal gradient process as well as the required parameters for an OSC to perform adequately in this treatment. As in the case of terthiophene, nucleation and growth can be decoupled for the other organic semiconductors depending on their rate of growth. Furthermore, we have been able to reproduce on another polymorphic compound the selective growth of a single polymorphic form by applying adequate gradient conditions. We have also observed that compounds tend to orient preferentially along one of their major morphological planes parallel to the substrate, indicating a heterogeneous nucleation mechanism. A careful comparison between the different samples allowed us to confirm and complete our growth mechanism proposition. Based on the undercooling, maximal growth rate, primary and secondary nucleation rates of the compound, geometry of the system and adequate gradient parameters, a preferential alignment of the crystals along the thermal gradient direction can be achieved. Finally, we showed through this investigation and careful comparison that 2,7-didodecyl[1]benzothieno[3,2-b][1]benzothiophene possesses all the characteristics to be an excellent material candidate for the thermal gradient processing: low primary nucleation rate, moderate undercooling, high growth rate, platelet-like crystal growth morphology and liquid crystal phase allowing preorganization of the compound before crystallization and processing on single substrates without dewetting. Moreover, this compound is currently one of the best solution processable organic semiconductors.<p>We then investigated the directional crystallization of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene directly from its liquid crystal phase as a function of thermal gradient parameters (magnitude of the gradient, sample velocity) and film thicknesses in thin film geometry (spin-coated films). Again, decoupling of the nucleation and growth has been observed for crystallization processed directly from the liquid crystal phase leading to the generation of highly textured films presenting uniaxial in-plane alignments of the crystallites. Moreover, secondary nucleation spots highlighted by POM in the alignment region give a clue to elucidate the alignment mechanism. The unit cell orients with the reciprocal vector c* normal to the substrate. Moreover, POM observation tends to indicate systematic thermal cracks orientations for higher rates of displacement (25 μm.s-1) as well as a reduction of the number of domains present in the sample, suggesting a preferential alignment of the crystallites at higher rates of displacement. All our results indicate that an optimum of the quality of the aligned film is reached for thermal gradient conditions of 120 °C - 90 °C - 25 μm.s-1. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The aim of this Thesis was on one side to contribute to a better understanding of the phases formed in the TiAlSiN(O) system and the influence of impurities on their properties. On the other side it was also aimed in the Thesis to individually study the phases forming the nanocomposite. <p><p>In each chapter the individual conclusions from that particular chapter are presented, a summary of the most relevant conclusions and achievements is listed below. <p><p><p>¡à\ / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The goal of this research is to improve an extractive metallurgy process based<p>on solvent extraction. This process should fit the exploitation of small local<p>copper-rich deposits. In these conditions, the plant has to be as compact as<p>possible in order to be easily transported from one location to a subsequent<p>one. Improved extraction kinetics could ensure a high throughput of the<p>plant despite its compactness. In addition, the extraction reagent should<p>not be damaging for the environnement. On this basis, we propose to use<p>ultrasound-assisted solvent extraction. The main idea is to increase the<p>extraction kinetics by forming an emulsion in place of a dispersion thanks to<p>the intense cavitation produced by ultrasound. The benefit of this method<p>is to improve the copper extraction kinetics by increasing the interfacial<p>surface area and decreasing the width of the diffusion layer. We studied the<p>implementation of an highly branched decanoic acid (known as Versatic-<p>10®acid) as a copper extraction reagent dispersed in kerosene.<p>Emulsification is monitored through the Sauter diameter of the organic<p>phase droplets in aqueous phase. This diameter is measured during pulsed<p>and continuous ultrasound irradiation via a static light scattering technique.<p>The phenomenon of emulsification of our system by ultrasound is effective,<p>and the emulsification process carried out in the pulsed ultrasound mode is<p>at least as efficient as the emulsification obtained under continuous mode.<p>No improvement of emulsification is observed beyond a threshold time of<p>the ultrasound impulse. This may be attributed to a competition between<p>disruption and coalescence. The use of mechanical stirring combined with<p>pulsed ultrasound allows to control the droplet size distribution.<p>In presence of ultrasound, the extraction kinetics of Versatic-10 acid is<p>multiplied by a factor ten, and therefore reached a value similar to the kinetics<p>observed without ultrasound with an industrial extractant such as<p>LIX-860I®(Cognis). Extraction kinetics measurements are carried out by<p>monitoring the copper ion concentration in the aqueous phase with an electrochemical<p>cell.<p>We conclude that ultrasound-assisted emulsification can be implemented<p>under certain conditions. Emulsification is a first step, and the following<p>destabilization step has to be studied. The device using ultrasound-assisted<p>emulsification should be followed by an efficient settling-coalescing device. A<p>possible solution would be to promote emulsion destabilization by increasing<p>the ionic strength with an addition of MgSO4, a salt that is not extracted<p>by the extraction reagent in the considered range of pH. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Since decades, drop impact has been a popular topic of investigation for the importance that such a phenomenology has in many different application domains.<p><p>So far, the effect of micro-particles on the drop impact morphology has been studied for a limited number of configurations and often modelled as a change in the viscosity of the carrier fluid. However, this approach has been found sometimes questionable. The aim of the thesis is to better understand the phenomenology associated with particle-laden drop impact such as the distribution of particles in splats and to extend the number of experimental configurations for particle-laden drop impact to occur.<p><p>The impact of millimetre-size particle-laden drops was investigated for hydrophilic and hydrophobic substrates. The drops were dispersions of water and round, spherical and nearly iso-dense hydrophobic particles with diameters around 200 µm and 500 µm. The substrates were transparent glass and polycarbonate plates. The impact was studied by side, bottom and angle view images in the range 148≤We≤744 and 7092≤Re≤16368.<p><p>The particles were found to suppress the appearance of singular jetting and drop partial rebound, and also cause early splashing, receding break-up and rupture. The occurrences of these phenomena depend on the impact velocity, particles’ diameter and volume fraction. The drops with 200 µm particles spread in two phases: fast and slow, caused by inertial and capillary forces, respectively. Also, the increase of volume fraction of 200 µm particle leads to a linear decrease of the maximum spreading factor caused by the inertia force on the hydrophilic and hydrophobic substrates. The comparison of our data and the existing ones for splashing led to the formulation of а new splashing criterion for particle-laden drops. The novel criterion improves upon current models in predicting the splashing threshold by introducing effect of particle volume fraction and particle wettability. The analysis of particle distribution showed that 200 µm particles formed atypical distributions in splats after the impact in contrast to 500 µm particles with random pattern. The 200 µm particles formed rings/disks and a crown-like structure on hydrophilic and hydrophobic substrates, respectively. These patterns were described by correlations.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The aim of the thesis is the development and improvement of the experimental techniques for fluid examination. The thesis consists of two parts and both examine heat and mass transfer in liquids using the optical methods and thermal analysis. The first part deals with the measurement techniques for studying flow patterns and their stability in systems with gas/liquid interface, in particular, in a liquid bridge system. The second part is aimed at the improvement of the existing experimental techniques to study the heat/mass transfer in the mixtures with Soret effect, enclosed in a container.<p><p>Part A is motivated by preparation of the experiment JEREMI (The Japanese-European Research Experiment on Marangoni Instability) to be performed on the International Space Station (ISS). One of the objectives of the experiment is the control of the threshold of an oscillatory flow in the liquid zone by the temperature and velocity of the ambient gas. The developed set-up for a liquid bridge allows to blow gas parallel to the interface at different temperatures and investigate the effects of viscous and thermal stresses on the stability of the flow. The present study reports on isothermal experiments with moving gas and non-isothermal experiments with motionless gas when the cooling of the interface occurs due to evaporation. The discussion concerning the experimental observations is based on two sources: an interface shape measured optically and the records on thermocouples giving an indication of how temperature and frequency evolve over time.<p><p>Part B is related to ground-based studies in course of preparation and realization of the microgravity experiment DCMIX (Diffusion Coefficient in MIXtures). DCMIX project is a series of experiments aimed at measuring of the Soret coefficients in liquid mixtures on the ISS which involves a wide international group of scientists. Two experiments have been recently completed and the third one is under preparation In the course of this thesis all the aspects of the previously existing set-up for measurements of the Soret (thermal diffusion) and diffusion coefficients in binary mixtures were studied, uncertainties were identified and improvements were done to obtain reliable results. The final design has been validated by measuring coefficients in three binary benchmark mixtures and water-isopropanol. The obtained results agree well with literature data. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Monoclonal antibodies (MAbs) have an expanding market for use in diagnostic and therapeutic applications. Industrial production of these biopharmaceuticals is usually achieved based on fed-batch cultures of mammalian cells in bioreactors (Chinese hamster ovary (CHO) and Hybridoma cells), which can express different kinds of recombinant proteins. In order to reach high cell densities in these bioreactors, it is necessary to carry out an optimization of their production processes. Hence, macroscopic model equations must be developed to describe cell growth, nutrient consumption and product generation. These models will be very useful for designing the bioprocess, for developing robust controllers and for optimizing its productivity.<p>This thesis presents a new kinetic model of hybridoma cell metabolism in fed batch culture and typical illustration of a systematic methodology for mathematical modelling, parameter estimation and model-based optimization and state estimation of bioprocesses. <p>In the first part, a macroscopic model that takes into account phenomena of overflow metabolism within glycolysis and glutaminolysis is proposed to simulate hybridoma HB-58 cell cultures. The model of central carbon metabolism is reduced to a set of macroscopic reactions. The macroscopic model describes three metabolism states: respiratory metabolism, overflow metabolism and critical metabolism. The model parameters and confidence intervals are obtained via a nonlinear least squares identification. It is validated with experimental data of fed-batch hybridoma cultures and successfully predicts the dynamics of cell growth and death, substrate consumption (glutamine and glucose) and metabolites production (lactate and ammonia). Based on a sensitivity analysis of the model outputs with respect to the parameters, a model reduction is proposed. <p>In the next step, the effort is directed to the maximization of biomass productivity in fed-batch cultures of hybridoma cells based on the overflow metabolism model. Optimal feeding rate, on the one hand, for a single feed stream containing both glucose and glutamine and, on the other hand, for two separate feed streams of glucose and glutamine are determined using a Nelder-Mead simplex optimization algorithm. Two different objective functions (performance criteria) are considered for optimization; the first criterion to be maximized is the biomass productivity obtained at the end of the fed-batch culture, the second criterion to be minimized is the difference between global substrate consumption and the maximum respiratory capacity.<p>The optimal multi exponential feed rate trajectory improves the biomass productivity by 10% as compared to the optimal single exponential feed rate. Moreover, this result is validated by the one obtained with the analytical approach in which glucose and glutamine are fed to the culture so as to control the hybridoma cells at the critical metabolism state, which allows maximizing the biomass productivity. The robustness analysis of optimal feeding profiles obtained with different optimization strategies is considered, first, with respect to parameter uncertainties and, finally, with respect to model structure errors.<p>Finally, the overflow metabolism model is used to develop an extended Kalman filter for online estimation of glucose and glutamine in hybridoma cell fed-batch cultures based on the considered available measurements (biomasses (on-line), lactate and ammonia (on-line or off-line)). The observability conditions are examined, and the performances are analysed with simulations of hybridoma cell fed-batch cultures. Glutamine estimation sensitivity is enforced by minimizing a cost function combining a usual least-squares criterion with a state estimation sensitivity criterion. <p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Le fruit de gac (Momordica cochinchinensis Spreng.) est un fruit traditionnel au Vietnam, lequel est extrêmement bénéfique pour la santé. L’arille de gac est une excellente source de caroténoïdes naturels, particulièrement le lycopène et le β-carotène. Ces composés antioxydants sont capables de neutraliser les radicaux libres et offrent des applications multiples, allant des effets généraux sur la santé à la prévention de certaines maladies chroniques. Ce travail a contribué au développement d’un procédé visant à la valorisation d’extraits du fruit de gac au Vietnam. Ce travail contient quatre parties principales: effet du semi-séchage sur les propriétés d’antioxydantes du fruit de gac; extraction de l’huile du fruit de gac assistée par enzymes; concentration des caroténoïdes de l’huile de gac par la filtration tangentielle; purification et cristallisation des caroténoïdes.<p>Dans la première partie, une étude du semi-séchage de l´arille de gac à différentes températures (40°C, 50°C, 60°C, 70°C et 80°C) et à trois modes de séchage (séchage à l’air, séchage sous vide et lyophilisation) a été effectuée pour déterminer l’effet de la mode, de la température et de l’humidité finale de séchage sur la couleur, la teneur en caroténoïdes totaux (TCC) et l’activité d’antioxydante totale (TAA) de l’arille de gac. Les résultats montrent que la lyophilisation permet une meilleure conservation permettant une valorisation ultérieure de la couleur, la TCC et la TAA de l’arille de gac. Le séchage sous vide donne les meilleurs résultats que le séchage à l’air. Une température entre 50°C et 60°C est optimale pour conserver la couleur, la TCC et la TAA de l’arille. Ces propriétés sont mieux conservées à l’issue d’un séchage permettant une humidité finale du produit de 15 à 18% (base sèche (db)) (semi-séchage) par rapport à 6% db. Le produit semi-séché peut être conservé pendant quelques mois. <p>Dans la deuxième partie, une étude d’optimisation d’extraction de l’huile de l’arille de gac assisté par des enzymes a été menée en utilisant la méthodologie de la surface de réponse. Un plan expérimental du type «design composite central» avec quatre variables indépendantes - la concentration en enzymes, le temps, la température et la vitesse d'agitation - a été réalisé. Les résultats montrent que ces quatre variables ont un effet significatif sur le rendement d’extraction de l’huile. Il n'y a pas d'interaction significative entre ces variables. Dans les conditions optimales obtenues (14,6% d’enzyme, 127 minutes, 58°C et 162 rpm), le rendement maximal de l’huile et la TCC obtenus sont de 79,5% et 5,3 mg/g de matière sèche, respectivement. Il existe une forte corrélation entre le rendement de l’huile obtenue et la TCC. Les propriétés physico-chimiques de l'huile extraite ont été déterminées. Enfin, les résultats du test Schaal montrent que le temps de conservation de l'huile extraite est comparable à d’autres huiles alimentaires, présentant le même type de profil en acides gras.<p>Dans la troisième partie, les caroténoïdes de l'huile ont étés concentrés à l'aide d'une filtration tangentielle, en utilisant une membrane céramique, selon deux modes de fonctionnement (recyclage total et batch). Dans les expériences en mode recyclage total, l'effet de la taille des pores de la membrane, la température et la pression transmembranaire sur le flux de perméat et le coefficient de rétention a été exploité. Les résultats montrent que ces facteurs ont un effet sur flux de perméat et le coefficient de rétention de la TCC, des phospholipides et des acides gras libres. La résistance intrinsèque de la membrane, la résistance de polarisation et la résistance liée au colmatage ont été estimées. Les conditions optimales déterminées sont 5 nm, 2 bars et 40°C, pour la taille des pores, la pression transmembranaire et la température, respectivement. En mode batch, le rétentat a été caractérisé en mesurant l'acidité, les phospholipides, la TCC, la TAA, des solides solubles totaux, la teneur en matières solides, la couleur et la viscosité de la solution. La TCC dans le rétentat est de 65,28 mg/ml (8,65 fois supérieure à celle dans l'huile d'alimentation). Les analyses de la TAA montrent que la contribution antioxydante principale de l'huile gac est lipophile. Après la filtration, la TAA lipophile du rétentat est 6,8 fois supérieur à celle de l’huile d’alimentation. L’analyse de la résistance indique que la résistance intrinsèque de la membrane représente 24% de la résistance totale. La majeure partie de la résistance est la résistance de polarisation (55%) tandis que la résistance de colmatage contribue pour 30%. <p>Dans la quatrième partie, les caroténoïdes provenant de l’huile du fruit de gac ont étés purifiés et cristallisés par une saponification combinée à l'utilisation de propylène glycol (un solvant moins toxique que les solvants organiques généralement utilisés). Ce processus est compatible à une consommation humaine, aux applications cosmétiques et plus respectueux de l'environnement que les procédés existants. Les résultats indiquent que l'utilisation de Tween 80 (0,05 ml/g d’huile) comme émulsifiant peut aider à augmenter la récupération des cristaux de caroténoïdes. La combinaison de 0,4 ml/g d'hydroxyde de potassium et 0,8 ml/g de propylène glycol donne un meilleur rendement de caroténoïdes. Une étude d’optimisation du processus de purification a été réalisée en utilisant la méthodologie de surface de réponse. Un plan expérimental du type «design composite central» avec trois variables indépendantes- la vitesse d'agitation, la température et le temps de réaction - a été effectué. Les résultats montrent que ces trois variables ont un effet significatif sur la récupération des caroténoïdes par cristallisation. Les interactions entre la vitesse d'agitation et la température ainsi qu’entre la température et le temps de réaction sont significatives. Dans les conditions optimales (1094 rpm; 46°C et 228 min), le rendement de caroténoïdes estimé est de 93,5%. Les cristaux de caroténoïdes contiennent 57,34% de lycopène et 36,67% de β-carotène. Ces résultats montrent que environ 85% et 78% du lycopène et du β-carotène, respectivement, ont étés récupérés.<p>Dans l’ensemble, cette thèse a contribué à la valorisation du fruit de gac au Vietnam, par une procédure de fabrication qui est économique et utilisant moins de produits chimiques. La recherche a permis de trouver les conditions optimales pour chaque étape de fabrication. Un nouvel axe de recherche pour valoriser le fruit de gac a été ouvert; il porte sur l’étude de l’application tant de l’huile de gac concentrée et riche en caroténoïdes naturels que des cristaux de caroténoïdes dans l’industrie alimentaire, pharmaceutique ou cosmétique.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Eutectoid steel strips are designed for the production of parts for intensive use such as clutches, seat slides, and springs as they exhibit<p>excellent strength levels and wear resistance. These properties arise from the unique morphology of lamellar pearlite which can be considered<p>as a self-laminated nanoscale composite. However, a spheroidization annealing step is nowadays necessary to improve the cold forming properties before further cold rolling steps.<p>This thesis is aimed at improving the tensile ductility of the hot rolled products of eutectoid composition in order to eliminate the intermediate<p>annealing step. Two strategies are proposed.<p>The first is to transpose the concept of controlled rolling developed for HSLA to<p>eutectoid steels. Through a strict adjustment of the austenite processing and of the cooling strategy, it is possible to improve the ductility<p>of the final lamellar microstructure. The way the processing parameters influence the hot deformation of austenite, the eutectoid transformation and of the subsequent spheroidization annealing is deeply<p>investigated. It is found that refinement and pancaking of austenite<p>is beneficial as it reduces the pearlite block size improving the total<p>tensile elongation. Accelerated cooling is of paramount importance to<p>achieve fine Interlamellar spacing (ILS), which lead to high strength<p>levels and accelerate spheroidization during subsequent annealing.<p>The second approach involves intercritical or warm deformation. Warm processing of eutectoid steels is first explored by torsion testing<p>and then up-scaled to a pilot rolling-line. The interactions between thermomechanical parameters, rolling forces generated and microstructural<p>evolution are carefully scrutinized. During concurrent hot deformation, spheroidization of cementite takes place almost instantaneously<p>in both torsion and rolling. The restoration processes occurring in the ferrite matrix depends on the strain path and the strain rates. Low strain rates (0,1 s−1) and simple shear promotes the formation of a recrystallized-like HABs network of about 3μm in size.<p>Plane strain compression and high strain rates (10 s−1) leads to the formation of a typical recovered dislocation substructure (LABs) of 1μm in size. During annealing, no recrystallization occurs and the LABs substructure remains stable. This substructure influences drammatically the mechanical properties: the strength is very high and the work-hardening behavior is poor due to high recovery rate in the region close to the LABs. However, due to the presence of spheroidized<p>cementite particles the ductility of warm rolled eutectoid steels is higher than that of ultra fine grained low carbon steels. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Le système ternaire eau-acide butyrique- pentan-2-ol est utilisé comme système modèle pour l’étude de système plus complexe. Ce système est utilisé pour étudier les couplages diffusifs quand les constituants sont distribués sur plusieurs phases. Ses molécules simples permettent de ne pas mettre en avant les effets stériques dus à de longues chaines carbonées ou entropiques dus à des importantes différences de masse moléculaire. <p>Les couplages de la diffusion avec la solubilité permettent d’observer toute une gamme de phénomènes allant de présence de turbidité ou de gouttelettes au sein de la phase aqueuse jusqu’au maintien de gradient de concentration bien au-delà du temps caractéristique de diffusion. Ces différents phénomènes ont été observés grâce à une expérience où l’on superpose deux phases de liquide, l’une de pentan-2-ol pur et l’autre d’un mélange d’eau et d’acide butyrique.<p>La solubilité du système est déterminée par une méthode RMN. Cette technique permet également d’obtenir les variations de l’environnement intermoléculaire avec la composition de la solution et de mettre en évidence des structures au sein du liquide. <p>Enfin les coefficients de self diffusion a été mesuré par méthode DOSY pour les liquides purs, les mélanges binaires et ternaires.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The main objective of this thesis is the development of new processing techniques for digital holograms. The present work is part of the HoloFlow project that intends to integrate the DHM technology for the monitoring of water quality. Different tools for an automated analysis of digital holograms have been developed to detect, refocus and classify particles in continuous fluid flows. A detailed study of the refocusing criterion permits to determine its dependencies and to quantify its robustness. An automated detection procedure has been developed to determine automatically the 3D positions of organisms flowing in the experiment volume. Two detection techniques are proposed: a usual method based on a global threshold and a new robust and generic method based on propagation matrices, allowing to considerably increase the amount of detected organisms (up to 95 %) and the reliability of the detection. To handle the case of aggregates of particles commonly encountered when working with large concentrations, a new separation procedure, based on a complete analysis of the evolution of the focus planes, has been proposed. This method allows the separation aggregates up to an overlapping area of around 80 %. These processing tools have been used to classify organisms where the use of the full interferometric information of species enables high classifier performances to be reached (higher than 93 %). / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished