Algunas aplicaciones de los plásticos en las industrias del empaque y automotriz

The role of plastic materials in the packaging and automotive industries is commented. Specific applications such as poly(ethylene-terephtalate) as gas barrier on the soft-drink bottle industry and low density polyethylene on the flexible packaging industry are presented. The use of polypropylene, high density polyethylene and polyamides are also mentioned.

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Caracterização microestrutural e elétrica de La(FexNi1-x)O3 sintetizado pelo método da gelatina

The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment

Influência de tratamentos térmicos no comportamento mecânico da blenda poli(metacrilato de metila) / poli(tereftalato de etileno) reciclado

Studies indicate that a variation in the degree of crystallinity of the components of a polymer blend influences the mechanical properties. This variation can be obtained by subjecting the blend to heat treatments that lead to changes in the spherulitic structure. The aim of this work is to analyze the influence of different heat treatments on the variation of the degree of crystallinity and to establish a relationship between this variation and the mechanical behavior of poly(methyl methacrylate)/poly(ethylene terephthalate) recycled (PMMA / PETrec) with and without the use of compatibilizer agent poly(methyl methacrylate-al-glycidyl methacrylate-al-ethyl acrylate) (MMAGMA- EA). All compositions were subjected to two heat treatments. T1 heat treatment the samples were treated at 130 ° C for 30 minutes and cooled in air. In T2, the samples were treated at 230 ° C for 5 minutes and cooled to approximately -10 ° C. The variation of the degree of crystallinity was determined by the proportional relationship between crystallinity and density, with the density measured by pycnometry. The mechanical behavior was verified by tensile tests with and without the presence of notches and pre-cracks, and by method of fracture toughness in plane strain (KIC). We used the scanning electron microscopy (SEM) to analyze the fracture surface of the samples. The compositions subjected to heat treatment T1, in general, showed an increase in the degree of crystallinity in tensile strength and a tendency to decrease in toughness, while compositions undergoing treatment T2 showed that the opposite behavior. Therefore, this work showed that heat treatment can give a polymer blend further diversity of its properties, this being caused by changes in the crystal structure

Processamento e caracterização da blenda poli (metacrilato de metila) (PMMA) elastomerico e poli (tereftalato de etileno) (PET) pós-consumo

This work studied the immiscible blend of elastomeric poly(methyl methacrylate) (PMMA) with poly(ethylene terephthalate) (PET) bottle grade with and without the use of compatibilizer agent, poly(methyl methacrylate-co-glycidyl methacrylate - co-ethyl acrylate) (MGE). The characterizations of torque rheometry, melt flow index measurement (MFI), measuring the density and the degree of cristallinity by pycnometry, tensile testing, method of work essential fracture (EWF), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were performed in pure polymer and blends PMMA/PET. The rheological results showed evidence of signs of chemical reaction between the epoxy group MGE with the end groups of the PET chains and also to the elastomeric phase of PMMA. The increase in the concentration of PET reduced torque and adding MGE increased the torque of the blend of PMMA/PET. The results of the MFI also show that elastomeric PMMA showed lower flow and thus higher viscosity than PET. In the results of picnometry observed that increasing the percentage of PET resulted in an increase in density and degree crystallinity of the blends PMMA/PET. The tensile test showed that increasing the percentage of PET resulted in an increase in ultimate strength and elastic modulus and decrease in elongation at break. However, in the phase inversion, where the blend showed evidence of a co-continuous morphology and also, with 30% PET dispersed phase and compatibilized with 5% MGE, there were significant results elongation at break compared to elastomeric PMMA. The applicability of the method of essential work of fracture was shown to be possible for most formulations. And it was observed that with increasing elastomeric PMMA in the formulations of the blends there was an improvement in specific amounts of essential work of fracture (We) and a decrease in the values of specific non-essential work of fracture (βWp)

Estudo da molhabilidade de tecidos 100% poliéster tratados em plasma N2/O2 em função do seu envelhecimento natural

This work reports the influence of the poly (ethylene terephthalate) textile surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min. Other parameters, such as working gas composition and treatment time, were modified as the following: to the O2 plasma modified samples only the treatment time was changed (10, 20, 30, 40, 50 and 60 minutes). To the plasma with O2 and N2 only the chemical concentrations were changed. Through Capillary tests (vertical) an increase in textile wettability was observed as well as its influence on aging time and its consequence on wettability. The surface functional groups created after plasma treatments were investigated using X-ray Photoelectron Spectroscopy (XPS). The surface topography was examined by scanning electron microscope (SEM)

Efeito da adição do poli(etileno acrilato de metila) (ema) e da fibra de linter de algodão nas propriedades do poli(tereftalato de etileno) reciclado (petrec)

The development of new materials to fill the demand of technological advances is a challenge for many researchers around the world. Strategies such as making blends and composites are promising alternatives to produce materials with different properties from those found in conventional polymers. The objective of this study is to evaluate the effect of adding the copolymer poly(ethylene methyl acrylate) (EMA) and cotton linter fibers (LB) on the properties of recycled poly(ethylene terephthalate) (PETrec) by the development of PETrec/EMA blend and PETrec/EMA/LB blend composite. In order to improve the properties of these materials were added as compatibilizers: Ethylene - methyl acrylate - glycidyl methacrylate terpolymer (EMA-GMA) and maleic anhydride grafted polyethylene (PE-g-MA). The samples were produced using a single screw extruder and then injection molded. The obtained materials were characterized by thermogravimetry (TG), melt flow index (MFI) mensurements, torque rheometry, pycnometry to determinate the density, tensile testing and scanning electron microscopy (SEM). The rheological results showed that the addition of the EMA copolymer increased the viscosity of the blend and LB reduces the viscosity of the blend composite. SEM analysis of the binary blend showed poor interfacial adhesion between the PETrec matrix and the EMA dispersed phase, as well as the blend composite of PETrec/EMA/LB also observed low adhesion with the LB fiber. The tensile tests showed that the increase of EMA percentage decreased the tensile strength and the Young s modulus, also lower EMA percentage samples had increased the elongation at break. The blend composite showed an increase in the tensile strength and in the Young`s modulus, and a decrease in the elongation at break. The blend formulations with lower EMA percentages showed better mechanical properties that agree with the particle size analysis which showed that these formulations presented a smaller diameter of the dispersed phase. The blend composite mechanical tests showed that this material is stronger and stiffer than the blend PETrec/EMA, whose properties have been reduced due to the presence of EMA rubbery phase. The use of EMA-GMA was effective in reducing the particle size of the EMA dispersed phase in the PETrec/EMA blend and PE-g-MA showed evidences of reaction with LB and physical mixture with the EMA

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

Avenues de synthèse d’un matériau magnétique multifonctionnel à des fins de catalyse hétérogène

La catalyse est à la base de la fabrication de médicaments, de produits textiles, d‘engrais, des pots d’échappement, et une multitude d’autres applications de notre quotidien. En effet, dans les pays industrialisés jusqu’à 80% des produits manufacturés utilisés au quotidien ont nécessité au moins une étape de catalyse lors de leur fabrication. Outre être actif, il est primordial pour un catalyseur performant d’être résistant à la désactivation qui se traduit par la perte d’activité ou de sélectivité d’un catalyseur au cours du temps. La synthèse d’un matériau multifonctionnel permet de répondre à ces différents critères. L’objectif d’un design intelligent de matériaux est de mener à des effets synergiques de chacune des composantes. Pour un catalyseur, en plus d’être actif et sélectif pour le produit désiré, il faut en plus qu’il soit durable, stable dans le temps, et permette d’être réutilisable. L’objectif de ce projet est de faire une synthèse originale, simple et reproductible d’un catalyseur actif et résistant à la désactivation. De base, un catalyseur se compose d’un support et d’un matériau actif. La nature, la morphologie et l’agencement de ces derniers dictent le comportement chimique du catalyseur final. Comme matériau actif, les nanoparticules d’or sont très prisées en raison de leur potentiel de catalyse élevée pour de nombreuses réactions. Cependant, aux températures de fonctionnement de la catalyse, les nanoparticules d’or ont tendance à se désactiver par coalescence. Pour remédier à cela, il est possible de déposer une couche de silice mésoporeuse afin de protéger les NPs d’or des rudes conditions de réaction tout en étant perméables aux espèces réactives. Plusieurs types de matériaux peuvent servir de support aux nanoparticules d’or. À ce titre, les particules d’oxydes de fer magnétiques telles que la magnétite (Fe[indice inférieur 3]O[indice inférieur 4]) sont intéressantes pour leur potentiel hyperthermique, phénomène par lequel des nanoparticules (NPs) magnétiques transforment de l’énergie électromagnétique provenant d’un champ externe haute fréquence en chaleur, créant ainsi des nano-fours. Une première couche de silice est utilisée comme matrice de greffage afin de fixer les nanoparticules d’or sur la magnétite. La structure visée est illustrée à la Figure ci-dessous. Figure 1 Structure du catalyseur de Fe2O4@SiO2-Au-SiO2m (Ge, Zhang, Zhang, & Yin, 2008) Plusieurs avenues d’assemblage et de synthèse sont explorées pour chacune des composantes de la structure visée. Les avantages et inconvénients ainsi que des mécanismes sont proposés pour chaque voie de synthèse. Le matériau est utilisé comme catalyseur pour la réaction de réduction du 4-Nitrophénol par du NaBH4. Pour ce qui est de la synthèse de magnétite par voie solvothermique, il a été démontré qu’il était important d’être dans un milieu sous pression puisque l’étape limitante de la réaction est la solubilité des particules de magnétites dans le milieu. Cela est en accord avec le principe de mûrissement d’Ostwald selon lequel les petites particules ont tendance à se dissoudre dans le milieu et précipiter à la surface des plus grosses particules de façon à diminuer l’énergie interfaciale. Cette synthèse a été reproduite avec succès et a mené à la production de nanoparticules de Fe[indice inférieur 3]O[indice inférieur 4] sphériques creuses d’une taille de 150 [plus ou moins] 30nm. Ces sphères creuses ont été recouvertes d’une couche de silice dense par une méthode de Stöber modifiée. Le recouvrement forme des amas de particules et est non uniforme en raison de la présence de poly(éthlyène glycol) à la sur face de la magnétite, un adjuvant présent lors de sa synthèse afin d’améliorer la dispersion de la magnétite. La synthèse et le greffage d’AuNPs sont bien maîtrisés : les AuNPs ont une taille de 17 [plus ou moins] 6nm et la quantité d’or greffé est assez élevée. Ultimement, une méthode de greffage alternative tel que le greffage par croissance in situ de nanoparticules d’or pourrait être emprunté afin d’obtenir des particules plus petites. Pour ce qui est de la formation d’une couche de silice mésoporeuse, la méthode par calcination est une meilleure option que par gravure chimique en raison de sa sélectivité envers la couche externe de silice plus élevée ainsi que la formation apparente de pores.

Preparação, caracterização e modificação de adsorventes para remoção de pesticidas de águas

O objectivo principal deste trabalho de mestrado consistiu em avaliar a potencial utilização de materiais adsorventes, nomeadamente, de carvões activados (AC) preparados por activação química com KOH, a partir de PET reciclado, e de materiais com estrutura mesoporosa ordenada, do tipo MCM-41 e SBA-15, na remoção de ácido 4 - cloro - 2 - metilfenoxiacético (MCPA) e de azul de metileno (MB), presentes nas águas. Nesta tese apresentam-se estudos de preparação e caracterização de materiais micro e mesoporosos e também estudos de avaliação da capacidade adsortiva em fase líquida. Prepararam-se três materiais microporosos, nomeadamente, PET-2-700, PET-2-700ox (AC oxidado) e PET-2-700red (AC reduzido), dois materiais constituídos exclusivamente por mesoporos, Si-MCM-41 e Ti-MCM-41-50 e dois materiais contendo maioritariamente mesoporos, mas que também possuem alguma microporosidade, tais corno, Si-SBA-15 e Ti-SBA-15-50. A caracterização textural dos adsorventes foi inferida por adsorção de azoto a 77K e por de difracção de raios X. Recorreu-se a três métodos de análise das isotérmicas, nomeadamente, Dubinin-Radushkevich, Brunauer-Ernrnett-Teller e alfa-s (as). A caracterização química dos AC foi realizada recorrendo-se a técnicas de análise elementar (AE) e espectroscopia de infravermelho com transformadas de Fourier (FTIR) e à determinação do ponto de carga zero. Os três carvões activados possuem valores de área superficial externa idênticos, o PET-2-700 possui o maior volume microporoso e o PET-2-700ox exibe o maior diâmetro de poros. Por outro lado, o PET-2-700ox possui um carácter fortemente ácido, o PET-2-700 exibe carácter ligeiramente ácido e o PET-2-700red apresenta propriedades ligeiramente alcalinas. Com base na AE, todas as amostras possuem percentagens de carbono elevadas, sendo que o PET-2-700red apresenta o valor mais elevado. Os resultados obtidos para a caracterização estrutural dos revelaram a obtenção de materiais mesoporosos de alta qualidade, definida pela elevada regularidade e uniformidade da estrutura porosa. A análise dos parâmetros de caracterização textura! permitiu inferir que os quatro materiais mesoporosos possuem valores de área superficial elevados, e que os materiais SBA-15 apresentam valores de volume poroso total e de tamanho de poros superiores aos manifestados pelos MCM-41. A incorporação de titânio não conduziu a uma perda significativa de qualidade dos materiais substituídos em relação às correspondentes amostras de sílica. Efectuaram-se estudos de adsorção em fase líquida de forma a avaliar a possível aplicação dos vários adsorventes na remoção de MCPA e de MB de efluentes líquidos. concluiu-se que o tempo de equilíbrio de 72 horas seria adequado e que a capacidade de adsorção dos vários AC era superior em meio ácido. Com base nas isotérmicas de adsorção do MCPA e do MB e na aplicação da representação de Langmuir e de Freundlich, foi possível concluir que o PET-2-700 possui a maior capacidade de adsorção do MCPA, 1.42 mmol/g, enquanto que o PET-2-700ox revelou a maior capacidade de adsorção do MB, 1.43 mmol/g. Na realidade, os materiais microporosos estudados apresentaram percentagens de remoção elevadas, tanto do MCPA como do MB. Relativamente aos materiais mesoporosos ordenados preparados neste trabalho, a percentagem de remoção de para os poluentes em estudo foi relativamente baixa, constatando-se que nesta fase dos estudos não constituem uma alternativa viável à utilização dos AC. No entanto, uma funcionalização criteriosa dos mesmos pode eventualmente proporcionar um aumento da capacidade adsortiva. ABSTRACT: The work presented in this master thesis, consisted of evaluating the potential use of different adsorbents materials, like activated carbon (AC) prepared by chemical activation with KOH, from recycled poly (ethylene terephthalate) (PET) and materials with ordered mesoporous structure such as MCM-41 and SBA-15, for removing acid 4-chlorine-2-metilfenoxiacétic and methylene blue from aqueous phase. We had prepared three microporous materials, PET-200-700, PET-2-700ox (AC oxidized) and PET-2-700red (reduced AC), two materials consisting exclusively of mesopores, Si-MCM-41 and Ti-MCM-41-50 and two materials containing mainly mesopores, but also having some microporosity, such as Si-SBA-15 and Ti-SBA-15-50. The textural characterization of the adsorbents was inferred by nitrogen adsorption at 77K and X-ray diffraction. Three methods were used to analyse the isotherms, namely, Dubinin-Radushkevich, Brunauer-Emmett-Teller and alpha-s (as). The chemical characterization of AC was performed using the elementary analysis, Fourier transform infrared spectroscopy (FTIR) and determination of the point of zero charge. Concerning the AC, the three present almost the same externa! surface area, PET-2-700 has a high micropore volume and PET-2-700ox shows the largest pore size diameter. On the other hand, PET-2-700ox had a strong acid character, PET-2-700 exhibits just a slightly acid character and PET-2-700red presents alkaline properties. The AE analysis allows confirming the high carbon content of theses AC, with PET-2-700red exhibiting the highest carbon proportion. The results from the structural characterization of the mesoporous materials, had disclosed the attainment of materials with high quality, defined by the raised regularity and uniformity of the porous structure. The analysis of the textural parameters allowed inferring that the four studied mesoporous materials possess high superficial area. The SBA-15 type materials present higher values of total porous volume and pores size diameter as the MCM-41. Also, the titanium incorporation did not lead to a significant loss of quality of the materials substituted in relation to the corresponding silica samples. The adsorption studies in liquid phase allow evaluating the possibility of using the different adsorbents for the MCPA and the MB removal. The kinetic studies had allowed to state the equilibrium time as 72 hours and a higher adsorption capacity was achieved in an acid medium. The influence of the pH of the medium, on the MCPA adsorption was evaluated. The MCPA and MB isotherms were analysed based on the Langmuir and Freundlich equation, the representations presented an excellent linearity, indicating the applicability of these equations to these systems. Also, it allows concluded that PET-2-700 had a higher adsorption capacity for MCPA, 1.42 mmol/g, and PET-2-700ox had a higher adsorption capacity for MB, 1.43 mmol/g. The AC used presented high removal percentages for MCPA and MB. Concerning the mesoporous materials prepared in this work, the percentage removal for the pollutants in study was relatively low, and evidencing that at the moment these mesoporous materials do not constitute a viable alternative to the AC. However, an astute funcionalisation of the same ones can, eventually provide an increase of the adsorption capacity.

Preparation and characterization of multifunctional bio-based polymers exhibiting enhanced properties

Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed.

Silicon nanocrystals tailored for bioimaging and energy conversion

This thesis focus is the development of hybrid organic-inorganic systems based on Silicon Nanocrystals (SiNCs) with possible applications in the field of bioimaging and solar energy conversion. SiNCs were engineered thanks to the realization of a strong covalent Si-C bond on their surface, which allowed us to disperse them in different solvents with different final purpose. Chapter 1 introduces the basic properties of nanomaterials. Chapter 2 describes all the synthetic procedures to obtain the organic molecules-functionalized SiNCs. Chapter 3 illustrates an organic-inorganic antenna system based on SiNCs conjugated with diphenylanthracene (DPA) photoactive molecules, which was also embedded into Luminescent Solar Concentrators (LSC) made of a polymeric matrix. The optical and photovoltaic performances of this device were compared with the ones of a LSC embedded with a physical mixture made of SiNCs plus DPA at the same concentrations of the two components in the covalent system. Chapter 4 shows many different techniques to functionalize SiNCs with polyethylene glycol (PEG) chains in order to make them dispersible in water, for biomedical imaging applications. Chapter 5 presents the synthesis of dyes and/or SiNCs loaded Polymer Nanoparticles (PNPs) capable of excitation energy transfer (EET) mechanism. Chapter 6 is focused on the realization of photo-switchable systems based on azobenzene derivatives-functionalized SiNCs. These organic-inorganic hybrid materials were studied to possibly obtain a new light-driven response of SiNCs. In the end, chapter 7 reports the activity I followed in America, at The University of Texas at Austin, in the laboratory led by the professor Brian Korgel. Here I studied and compared the properties of high temperature hydrosilylated SiNCs and room temperature, radical promoted, hydrosilylated SiNCs.

Sinthesys of heteroleptic zinc complexes for imaging in living cells

This thesis arose from an interest in luminescence heteroleptic bis(dipyrrinato) Zn (II) complexes and their application in cell imaging, due to their attractive and fascinating characteristics. Among imaging technologies, near-infrared fluorescence imaging has been dedicated immense attention owing to its low absorption and autofluorescence from surrounding organism and tissues in this specific spectral region, which minimize background interference and improve tissue depth penetration. An ideal near-infrared probe should be equipped with excellence chemical and photophysical properties. The target of this work is the synthesis of new heteroleptic bis(dipyrrinato) Zn (II) complexes having two main features: the emission in the near-infrared region and water-solubility. In order to purse these intentions, the low-energy emission was achieved by expansion of π-conjugation of simple dipyrrins using Knoevenagel condensation106 and tri(ethylene)glycol chain was introduced to increase the water solubility of the final complex. Photophysical and luminescent properties of the new complexes were investigated. Finally, with a view to a potential biological use of these new complexes in biological environments, their biocompatibility was tested using a cell viability assay: (3-(4,5-dimethylthiazol-2-yl)-2’-5’-diphenyltetrazolium bromide (MTT) assay.