Magister Scientiae - MSc (Chemistry) / This work involves the synthesis of copper telluride-polypropylenimine tetra(5-(2-thienyl) salicylaldimine) (CuTe@PPI) and copper antimonide-polypropylenimine tetra(5-(2-thienyl) salicylaldimine) (CuSb@PPI) core-shell nanoparticles (NPs), using two-pots and one-pot synthesis methods, respectively. Their morphology was studied by X-ray diffraction spectroscopy (XRD), high resolution transmission electron microscopy (HRTEM) and high resolution scanning electron microscopy (HRSEM); while their structures were characterized by Fourier transform infrared spectroscopy (FTIR) and elemental analysis. Photophysical properties of the core-shell NPs were determined from ultraviolet-visible absorption spectroscopy (UV-Vis) and photoluminescence spectroscopy (PL). For core-shell NPs produced via two-pots method only CuTe@PPI exhibited ? ? ?* and n ? ?* which indicate that CuSb@PPI produced via two-pots method was unsuccessfully synthesized. The ? ? ?* and n ? ?* transitions indicate the presence of polypropylenimine tetra(5-(2-thienyl) salicylaldimine) (PPI) on the surface of CuTe NPs and CuSb NPs. FTIR confirmed coordination of PPI on the surface of CuTe NPs and CuSb NPs by showing a shift in wavenumber of C=N group bands from PPI. HR-TEM showed that the CuTe@PPI synthesized via one-pot method have a wide particles sizes distribution with an average particles size of 13.60 nm while for CuTe@PPI synthesized via two-pots it was impossible to determine the particles size due to aggregation. CuSb@PPI synthesized via twopots method and one-pot method has a wide particles sizes distribution with an average size of 7.98 nm and 11.61 nm respectively. The average particles sizes determined by HR-SEM were found to be 35.24 nm (CuTe@PPI two-pots method), 33.90 nm (CuTe@PPI one-pot method), 18.30 nm (CuSb@PPI two-pots method), and 16.18 nm (CuSb@PPI one pot method). / 2021-08-31

O objetivo do trabalho foi sintetizar e caracterizar nanopartículas de poliestireno e polimetacrilato de metila com morfologia núcleo-casca obtidas através da polimerização em emulsão sem emulsificante em dois estágios e através da fotopolimerização. Nos experimentos avaliou-se a influência de diferentes condições operacionais baseadas em fatores cinéticos sobre os dois estágios da polimerização. As condições avaliadas para o primeiro estágio de preparação de núcleos foram: a temperatura do processo, a concentração de iniciador e de monômero, e o efeito de agentes modificadores de superfície (sal, co-monômero e reticulante). Para o segundo estágio de formação da casca as condições avaliadas foram: a concentração e o regime de alimentação de monômero. Os resultados experimentais mostraram que uma relação de co-monômero e reticulante é a melhor alternativa para preparar núcleos estáveis e de diâmetros pequenos. Assim, o revestimento uniforme dos núcleos é obtido no segundo estágio e com isso a morfologia núcleo-casca em equilíbrio é alcançada. Dois sistemas experimentais (reator convencional e reator fotoquímico) foram propostos e avaliados na sua eficiência para obter partículas com este tipo de morfologia no segundo estágio (formação do revestimento). As diversas técnicas de caracterização indicaram a formação de morfologia núcleo-casca na maioria dos casos estudados para os dois sistemas propostos. Por sua vez, as técnicas espectroscópicas (NIR e Raman) permitiram o monitoramento do processo em tempo real e a elaboração de modelos de calibração que correlacionaram o crescimento do tamanho da partícula núcleo. Da mesma forma, os fatores termodinâmicos foram estudados para predizer a morfologia final esperada nos sistemas. Os resultados, experimental e predito são comparados e discutidos em termos de aspectos chave envolvidos no controle da morfologia da partícula. / This work aimed at studying the synthesis and characterization of core-shell nanoparticles of polystyrene and polymethylmethacrylate obtained in a two-stage emulsifier-free emulsion polymerization and photopolymerization. The influence of different operational conditions based on kinetic factors was experimentally evaluated. In the first stage (seed preparation) the process temperature, initiator and monomer concentrations and the effect of surface-modifier agents (acids, salts, co-monomers and crosslinker) were investigated; similarly in the second stage, the concentration and feeding regime of monomer were evaluated with respect to the shell formation. Experimental results showed that both, crosslinker and co-monomer are the best alternative to achieve a stable seed with small diameter; hence, with this core, uniform coating is obtained in the second stage and core-shell morphology is reached. In order to evaluate the efficiency of the preparation of core-shell particles, two experimental systems (conventional and photochemical reactor) were studied. Different characterization techniques indicated that in most of the cases studied particles with the desired core-shell morphology were formed. The use of spectroscopic techniques NIR and Raman were tested for the real-time monitoring of the process using adequate calibration models developed to correlate the average size of the growing core particle with the spectra. In the same way, thermodynamic factors were used to predict the expected final morphology of the particles. Experimental and predicted results were compared and discussed in terms of the key aspects involved in the control of the particle morphology.

L'objectif de la présente thèse est d'améliorer les propriétés barrières du MetPET en conditions sévères. Plus précisément d'établir les corrélations structure-propriétés : structure du primaire d'accroche déposé en ligne sur le film PET avant métallisation et propriétés barrières et d'adhésion métal en condition sèche et humide du composite final obtenu (MetPET). L'approche choisie est la polymérisation en émulsion en régime semi-continu. Cette approche permettra d'apporter un caractère hydrophobe (phase 1-Coeur) favorisant la barrière à l'humidité et un caractère hydrophile (phase 2-Ecorce) en surface présentant des groupes fonctionnels favorables à l'adhésion métal en condition humide. De plus nous avons aussi investigué l'influences de divers additifs de formulations afin d'optimiser les propriétés du primaire d'accroche. Les latex présentant une structure de type cœur/écorce est très favorable pour la barrière à l'humidité. En effet ces latex présentent une perméabilité à l'eau sensiblement plus faible que les latex sans structure (100% composition de l'écorce). Concernant la perméabilité à l'oxygène celle-ci est principalement assurée par la couche métallique. La formulation de nos latex cœur/écorce par des agents mouillants s'est révélé indispensable pour assurer un bon étalement de nos latex sur le substrat PET. En effet nos latex issus de la synthèse ont été synthétisés avec un minimum de tensio-actif, ce qui a eu pour effet négatif d'obtenir une tension de surface trop élevée pour assurer leur mouillabilité sur le film PET. De plus cet agent mouillant a aussi montré une influence positive sur les performances d'adhésion de la couche métal sur le film PET traité avec le primaire d'accroche. La formulation de nos latex cœur/écorce par un réticulant a montré un influence positive sur les propriétés barrières aux gaz et sur les performances d'adhésion métal. Cet agent réticulant tend à favoriser la réticulation entre particule et ainsi favoriser la formation d'un film continu barrière à l'eau. De plus celui-ci apporte des fonctions de type azoté favorable aux interactions avec les atomes métallique (aluminium) / The proposition of this work is to improve the barrier property of a laminate aimed to be applied in the field of packaging for foodstuffs. This laminate is constituted by a PET substrate metallized with aluminum deposited under vacuum. Given that PET is not a strongly polar polymer it is necessary to improve its adhesion to metals. This study was carried out in order to understand if there is a way to make sure that the polar groups will be bonded to the metal without being disturbed by the conditions of the environment. Our approach was the semi-batch emulsion polymerization, followed by the restructuration of the initial system (regular spherical polymeric nanoparticles) by changing its original morphology. Finally, the latexes were formulated by using variable amounts of compounds that were expected to improve the properties of the final material in terms of barrier and metallic adhesion. A part of the latexes synthesized in the scope of this work was submitted to pilot trials in an industrial line of PET extrusion. The latexes were used to coat the PET inline. The core-shell nanoparticles presented a lower permeability to water than the particles synthesized in the absence of the seed. This was related to the tortuosity promoted by the core, which increases the pathway of a diffusing molecule. The permeability to oxygen was found to be mainly related to the metallic layer. Given that the latexes were synthesized with the minimum amount of tensioactive necessary to originate stable dispersions, the wettability agent was found to be indispensable for the proper spreading of the coatings onto the PET. Furthermore, this compound played an important role on the adhesion property of the films. The cure agent, in the correct concentration, promotes the adhesion to metallic substrates. Moreover, this compound helped to prevent the interaction of the wettability agent with the water, decreasing consequently the plasticization of the structure in conditions of high humidity

Les contextes mondiaux énergétiques, climatiques et économiques actuels évoluent de manières telles que le dihydrogène H2 prend une place de plus en plus importante en tant que combustible et vecteur énergétique. Le dihydrogène est un gaz incolore, inodore et non-toxique donc indécelable par les sens humains, mais il est extrêmement inflammable et explosif. De plus, H2 est caractérisé par un domaine d'explosivité très large, de 4 % à 75 % de H2 dans l'air. L'objet de ce travail de thèse a donc été de préparer des capteurs de sécurité ou de quantification originaux et ayant des performances accrues pour la détection de H2. Les capteurs préparés sont de types résistifs et les métaux sensibles utilisés sont le palladium et le platine. Afin d'améliorer les performances de détection de ces capteurs à dihydrogène, plusieurs morphologies de couches sensibles ont été conçues : des monocouches organisées à 2 dimensions de nanoparticules cœurs-coquilles Pd@Au et Pt@Au formées par la méthode de Langmuir-Blodgett ou immobilisés sur les substrats par un agent de couplage de type silane (mercaptopropyltrimethoxysilane), des dépôts physiques à 2 dimensions et des films de nanoparticules à 3 dimensions. Selon la morphologie de la couche préparée et le type de métal sensible utilisé, divers mécanismes de détection ont été mis en évidence et diverses performances de détection ont été observées (type et amplitude de réponse, gamme de détection, temps de réponse et de retour,...). Les modèles de Fuchs-Sondheimer et Mayadas-Shatzkes d'une part, et un modèle de percolation par la création de chemins de conduction d'autre part, ont permis d'expliquer les variations de résistivité électrique des couches sensibles à base respectivement de platine et de palladium lors de l'exposition à l'hydrogène. / Hydrogen takes is foreseen as a generalized fuel and energy carrier. It is a colorless, odorless and non-toxic gas, and therefore it is undetectable by the human senses. Hydrogen has a severe drawback as it is an extremely flammable and explosive gas. Moreover, H2 has a wide explosive range, from 4 to 75 % H2 in air. Therefore, the aim of this PhD work was to develop safety and concentration sensors with enhanced performances. Resistive sensing layers were designed on several morphologies and sensing materials : 2D Langmuir-Blodgett organized monolayers of core-shell Pd@Au or Pt@Au nanoparticles, immobilized Pd@Au monolayer grafted through a self assembled monolayer, evaporated 2D metal films of Pt or Pd, and 3D platinum nanoparticles arrays. According to the sensing layer morphology and sensing metal, numerous sensing mechanisms and performances were demonstrated (response type and amplitude, sensing range, response and recovery times,…). Fuchs-Sondheimer and Mayadas-Shatzkes models on the one hand, and a percolation model on the other, allowed the origin of electrical resistance changes to be pointed out, respectively for platinum and palladium sensing layers.

L’exaltation de fluorescence par un métal est de plus en plus utilisée pour augmenter la sensibilité de détection dans les systèmes utilisant la fluorescence. Au cours de ce travail de thèse, nous avons étudié ce phénomène dans des nanoparticules hybrides Métal@SiO2 possédant des émetteurs de fluorescence immobilisés sur la silice. Dans un premier temps, nous avons élaboré les nanoparticules cœur-coquille Métal@SiO2 (Métal = Au ou Ag) en utilisant différentes méthodes et en les comparant pour choisir la plus adaptée selon le diamètre du cœur métallique. Dans un deuxième temps, nous avons étudié les propriétés de fluorescence exaltée des nanoparticules hybrides. Deux types d’émetteurs de fluorescence ont été sélectionnés : des nanoparticules semi-conductrices (SiC) et des fluorophores organiques (cyanine 3 et fluorescéine). Après fonctionnalisation de la silice, les émetteurs de fluorescence ont été greffés à la surface des nanoparticules Métal@SiO2. L’exaltation de leur fluorescence a été analysée en fonction de leur densité surfacique, de leur distance par rapport au cœur métallique (fixée par l’épaisseur de silice), du diamètre du cœur métallique et de la longueur d’onde d’excitation. Le facteur d’exaltation le plus important (de l’ordre de 103) a été obtenu avec une faible épaisseur de silice (10 nm) pour les nanoparticules de SiC dont le rendement quantique intrinsèque est très faible (inférieur à 1%). Enfin, la surface de nanoparticules hybrides a été fonctionnalisée avec des nanoparticules d’oxyde de fer de manière à obtenir une combinaison de propriétés optiques (fluorescentes et plasmoniques) et magnétiques à l’intérieur d’une même nanoparticule hybride. / For the past decade, metal-enhanced fluorescence (MEF) has attracted much attention as it improved the sensitivity of fluorescence detection. In this work, MEF was investigated in hybrid Metal@SiO2 nanoparticles with fluorescent emitters immobilized onto silica. In the first part, core-shell Metal@SiO2 (Metal = Au or Ag) nanoparticles were elaborated and several elaboration methods were compared. A comparison was given in order to choose the most suitable method depending on metal core diameter. The second part was dedicated to MEF properties of hybrid nanoparticles. Two kinds of fluorescent emitters were selected: quantum dots (SiC) and organic dyes (cyanine 3 and fluorescein). After silica surface modification, fluorescent emitters were linked to Metal@SiO2 nanoparticles. MEF phenomenon was investigated by tuning the distance between metal and fluorescent emitter (fixed by silica thickness), metal diameter, the fluorescent emitter surface density, and the excitation wavelength. The highest enhancement factor (almost 103) was obtained for a low silica thickness (10 nm) with SiC nanoparticles whose intrinsic quantum yield is very low (lower than 1%). Finally, we functionalized the surface of hybrid nanoparticles with iron oxide nanoparticles to obtain a combination of optical (fluorescence and plasmonics) and magnetic properties inside one hybrid nanoparticle.

De nouveaux matériaux à base de silice (silice mésoporeuse SBA-15 et nanoparticules coeur-coquille) associés à des hybrides de polyoxométallates lacunaires ont été élaborés pour des applications relavant de la catalyse homogène supportée, lors de réactions d'oxydation douce. Le critère principal a été la formation de liaisons covalentes entre les POMs et les deux types de supports utilisés. Des POMs à structure de Keggin portant des fonctions acide carboxylique ont été greffés sur des SBA-15 fonctionnalisées par des amines. Ce même support a été ensuite utilisé pour d'autres stratégies d'immobilisation covalente, comme l'utilisation d'un agent de réticulation. En parallèle, des nanocatalyseurs hybrides on été synthétisés par l'association de nanoparticules coeur-coquille magnétiques et de POMs. Tous ces matériaux ont été caractérisés par une large gamme de techniques physicochimiques. L'utilisation de la microscopie électronique par transmission haute résolution a permis de localiser les POMs à l'intérieur des pores de la SBA-15 et à la surface des nanoparticules magnétiques, montrant ainsi une très bonne nanostructuration à leur surface. L'activité catalytique des catalyseurs homogènes supportés synthétisés a été évaluée au travers de l'époxydation du cyclooctène et du cyclohexène par H2O2 dans l'acétonitrile. De bonnes conversions ont ainsi été obtenues dans certains cas, en comparaison avec les systèmes homogènes testés lors de ce travail. Une attention particulière a été portée aux bonnes performances catalytiques du POM portant des fonctions acide carboxylique. Des calculs DFT ont ainsi été réalisés afin d'identifier la cause de cette réactivité particulière. / New materials based on silica oxides (mesoporous silica SBA-15, magnetic core-shell nanoparticles) combined with nucleophilic hybrids of (vacant) polyoxometalates were elaborated for applications in the field of anchored homogeneous catalysis for mild oxidations reactions. The main parameter taken into account was the formation of a covalent bond between the support and the POMs. Two different pathways were followed depending upon the support used for the covalently grafting of POMs. Firstly, Keggin type POMs bearing carboxylic acid functions were grafted onto amino-functionalized SBA-15. Using the same support, other covalent immobilization methods were tried out, such as the use of a cross-linker. Secondly, hybrid nanocatalysts based on magnetic core-shell nanoparticles grafted with POMs were synthesized. All materials were characterized by a wide variety of physicochemical techniques. By HR TEM, the POMs were localized inside the pores of SBA-15 and onto the surface of magnetic core shell NPs, showing an excellent nanostructuration on the surface of both materials. Furthermore, the catalytic activity of the synthesized anchored homogeneous catalysts has been evaluated through the epoxidation of cyclooctene and cyclohenexe with H2O2 in acetonitrile, resulting in fairly good conversions in some cases, compared to the homogeneous systems used in this study. Finally, particular attention was paid to the excellent catalytic behavior of POMs bearing carboxylic acid functions compared to other POMs of the same family. Thus, DFT calculations were performed in order to identify the cause of this enhanced reactivity.

The aim of this master thesis is synthesis of SiO2/Au core/shell nanoparticles. These nanoparticles should improve the signal of optical coherence tomography (OCT). The procedure of nanoparticle synthesis is described in the work. Synthetized nanoparticles were analyzed by scanning electron microscopy (SEM), Ultraviolet-Visible spectroscopy (UV-Vis), Near-infrared spectroscopy (NIRS), Fourier transform-infrared spectroscopy (FT-IR) and Dynamic light scattering (DLS). Then, the synthetized nanoparticles were tested for enhancement of OCT signal. For this testing were also used commercial nanoparticles with the same structure and similar size.

No description available.

This thesis provides several nanomaterial systems that can be used as contrast agents in magnetic resonance imaging (MRI) and for optical fluorescence imaging. Nanoparticle systems described in this thesis fall under three categories: (a) graphene oxide-nanoparticle composites for MRI contrast agent application, (b) core-shell nanoparticles for MRI contrast agent application and (c) nanoparticle systems for both MRI and optical fluorescence imaging. In the case of graphene oxide based nano-composites, the following observations were made: (i) in the case of graphene oxide-Fe3O4 nanoparticle composite, it was observed that high extent of oxidation of the graphene oxide and large spacing between the graphene oxide sheets containing Fe3O4 nanoparticles provides the optimum structure for yielding a very high transverse proton relaxivity value, (ii) in the case of graphene oxide-Gd2O3 nanoparticle composite, it was observed that this composite exhibits high value for both longitudinal and transverse relaxivity values making it a potential materials for multi-contrast study of pathologies with a single agent, (iii) in the case of graphene oxide-CoFe2O4 nanoparticle composites, it was observed that an increase in the reflux time of the reaction mixture containing this composite led to appreciable variations in the proton relaxivity values. Transverse relaxivity value of the water protons increased monotonically with increase in the reflux time. Whereas, the longitudinal relaxivity value initially increased and then decreased with increase in the reflux time. In the case of coreshell nanoparticles for MRI contrast agent application two different core-shell systems were investigated. They are MnFe2O3-Fe3O4 core-shell nanoparticles and CoFe2O4-MnFe2O4 coreshell nanoparticles. Investigations of both the core-shell nanoparticle systems revealed that the proton relaxivity value obtained in the dispersion of the core-shell nanoparticles was considerably greater than the proton relaxivity value obtained in the presence of single phase nanoparticles of the core and shell phases. Very high value of transverse relaxivity in the case core-shell nanoparticles was due to the large magnetic inhomogeneity created by the core-shell nanoparticles in the water medium surrounding it. In the case of nanoparticle systems for both MRI and optical fluorescence imaging, two different systems were investigated. They were CoFe2O4-ZnO core-shell nanoparticles and Gd doped ZnS nanoparticles [Zn1-xGdxS, x= 0.1, 0.2 and 0.3] formed on graphene oxide sheets or coated with chitosan. In the case of CoFe2O4-ZnO core-shell nanoparticles it was observed that fluorescent CoFe2O4-ZnO core-shell nanoparticles with the unique geometry in which CoFe2O4 ferrite nanoparticles agglomerates were present within larger sized hollow ZnO capsules yields very high value of transverse proton relaxivity when compared to the proton relaxivity value exhibited by the individual CoFe2O4-ZnO coreshell nanoparticles. In the case of Gd doped ZnS nanoparticles, two different systems were synthesized and the values of the longitudinal and transverse proton relaxivity obtained were compared. These systems were (i) graphene oxide- Zn1-xGdxS (x= 0.1, 0.2 and 0.3) nanoparticle composites and (ii) chitosan coated Zn1-xGdxS (x= 0.1, 0.2 and 0.3) nanoparticles. It was observed that Gd doped ZnS nanoparticles in both cases exhibit both longitudinal and transverse relaxivity values. The relaxivity values showed a clear dependence on the composition of the nanoparticles and the nanoparticle environment (presence and absence of graphene oxide). It was also observed that Gd doped ZnS nanoparticle can be used for florescence imaging.

Le poly (acide lactique) (PLA), est un polymère synthétisé à partir de ressources renouvelables, qui est l'objet de beaucoup d'études à l'heure actuelle mais qui souffre d'une faible résistance au choc. Le but de ce travail est de rechercher des pistes permettant la préparation d'un matériau à base de PLA avec une résistance au choc améliorée tout en minimisant la perte de résistance à la traction. Les travaux présentés ici ont étudié le rôle de nanoparticules élastomères de poly (acrylate de butyle) (PBA) chargées de laponite (LRD) (PBA-LRD) ainsi que de nanocomposites coeur-écorce (PBA-LRD)/poly(méthacrylate de méthyle) (PMMA) en tant qu'agents de renforcement d'une matrice de PLA. Ces nanoparticules ont été dispersées dans la matrice PLA à l'état fondu. La synthèse de ces nanoparticules a été effectuée par polymérisation en émulsion ou miniémulsion. La laponite a été incorporée dans les nanoparticules afin de minimiser la perte de la rigidité tout en améliorant la résistance au choc de PLA. Trois types de tensioactifs et des modifications de surface de la laponite ont été testées pour améliorer l'adhérence entre les particules de PBA et la matrice de PLA. Enfin une écorce de PMMA a été utilisée pour assurer la bonne adhérence entre les particules de PBA et de matrice PLA. Nous avons montré que les particules coeur-écorce ont permis d'augmenter la résistance au choc au 3 fois du PLA tout en réduisant la diminution du module d'Young et la perte de résistance à la traction (~25%). Les propriétés de les particules synthétiques et les propriétés des mélange du PLA avec les particules PBA ou particules coeur-écorce ont été étudiées par diverses techniques de caractérisation (DLS, FTIR, ATG, MET, MEB, RMN 1H, DSC, DMTA...) / Poly (lactic acid) (PLA), come from renewable resources, one of the most important biopolymers, suffers from weak impact resistance. The aim of this work is to develop a process that will allow preparing a PLA with improved impact resistance while minimizing loss in tensile strength. The work presented here examined in detail the synthesis of poly(butyl acrylate) (PBA) nanoparticles charged with laponite (LRD) (PBA-LRD) and (PBA-LRD) / poly(methyl methacrylate) (PMMA) core-shell nanocomposites. They were dispersed phase in PLA matrix and were synthesized by emulsion or miniemulsion polymerization. The clay such as laponite was included in these nanoparticles to minimize the loss of rigidity while improving the impact resistance of PLA. Note that three types of surfactants and some modify agents for LRD have been tried to improve the adhesion between the PBA particles and matrix PLA, PMMA was finally used to ensure a good adhesion between the PBA particles and the matrix. To this end, we explored successively the PLA blend, using PBA nanocomposites and the PBA/PMMA core-shell nanoparticles as reinforcing agents, with improved impact resistance, showing that core-shell particles allowed increasing of 3 times of impact strength of the PLA with a minimum amount of loss (~25%) in Young?s modulus and tensile strength. The properties of the synthetic particles and the properties of PLA blends have been demonstrated by various characterization techniques (DLS, FTIR, TGA, TEM, SEM, 1H-NMR, DSC, DMTA ...)