Spent oil based drilling fluid and cutting wastes are global liabilities due to their hazardous hydrocarbon content which impacts negatively on flora, fauna, and global carbon footprint. The formulation of two demulsifiers to ensure chemically enhanced phase separation of this waste into oil, water and solid components was successfully carried out in addition to recycling the solid phase into PA6 nanocomposite materials. Initial characterisation of the untreated waste was carried out by Fourier Transform Infra Red (FTIR) for total petroleum hydrocarbon (TPH) analysis, Inductively coupled plasma optical emission spectrometry (ICPOES) for quantitative elemental analysis and Energy dispersive xray analysis (EDXA) for qualitative elemental composition amongst other characterisation methods. The analysis showed that the sample had a high hydrocarbon load of 662,500mg/kg and a high heavy metal load for Pb of 122mg/kg. No As, Cd, Hg were detected. The demulsifier formulations were composed of isopropanol, sodium dodecyl sulphate, poloxamer, sodium chloride, chitosan in 0.2M acetic acid and deionised water for demulsifier S4 and addition of phosphoric acid for demulsifier S3. Hydrocarbon reduction on the extracted solid phase nanofiller S3 and nanofiller S4 was 98.6% and 98.5% respectively after demulsification. The demulsified spent oil based drilling fluid solid extracts were below OSPAR regulation of < 1% oil on cutting by weight. However, recycling of the recovered solid was carried out in order to achieve environmentally sustainable management of the waste in Polyamide 6 (PA6) nanocomposite manufacture/fabrication. The formulation of different blends of PA6 nanocomposite materials from untreated, demulsifier treated and thermally treated drilling fluid and cuttings was successfully achieved. Nanocomposite leaching test showed Pb immobilisation. The flexural and compressive - modulus and strength of the PA6 were markedly improved in the presence of the nanofillers and glass fibre. This was attributed to the reinforcement, exfoliating, stiffening, rigidity effect of the nanofillers. S6 (untreated drilling fluid) nanofillers significantly improved the mechanical properties of PA6. This was attributed to the increased interfacial bonding between the fillers and the polymer matrix as a result of the petroleum hydrocarbon present in the sample. The Thermogravemetric analysis (TGA) results showed that nanocomposites PA6/S3 and PA6/S3/GF30 had improved the thermal stability of PA6 by 13.6% and 38.8% respectively compared to PA6/S2 and PA6/S2/GF30 (simulated commercial nanocomposite materials) that improved PA6 by 9.7% and 35.8% respectively.

Noble metal incorporated MCM-41 based nanostructured mesoporous materials have attracted the attention of material researchers in recent years. Sorption characteristics of MCM materials can be improved by surface modification techniques. Besides surface modification, metal nanoparticles can also be produced within the pores of mesoporous materials. MCM-41 can act as host for several metal nanoparticles such as palladium. The present study is focused on the synthesis of Pd-MCM-41 nanocomposite catalytic materials by using different direct synthesis procedures, as well as an impregnation method. Impregnated samples were used to synthesize Pd nanoparticles inside the pores of MCM-41. In the direct hydrothermal synthesis of Pd-MCM-41, incorporation of the Pd metal was achieved by adding PdCl2, K2PdCl4 and Pd(NH3)4(NO2)3 solutions into the synthesis mixture. Syntheses were performed in acidic and basic routes. Hydrothermal synthesis was carried out in an autoclave at 120 oC. The solid product was filtered, washed, dried, calcined at 550 oC in a stream of dry air and reduced in a stream of hydrogen at 200 oC. In the case of impregnation, PdCl2 solution was added to a suspension of MCM-41. The product was evaporated to dryness, dried under vacuum and reduced with H2 gas at 200 oC. Physical and chemical properties and surface morphology of Pd-MCM-41 nanomaterials were characterized by using XRD, XPS, EDS, BET, SEM, TEM and TPR techniques. Very high Pd/Si ratios, as high as 0.45 and 0.18 were obtained in the mesoporous materials produced by the basic and acidic direct synthesis routes, respectively. The BET surface areas of these materials were found as 999 m2/g and 694 m2/g, respectively. These results showed that the basic direct synthesis procedure was highly successful for the incorporation of Pd into the mesoporous Si structure. In addition, EDS analysis of the Pd-MCM-41 materials prepared by the impregnation technique showed that Pd/Si ratios were 0.24 and 0.12 in the two samples having surface areas of 527 m2/g and 883 m2/g, respectively. In conclusion, high surface area of the material synthesized by the basic route together with a higher Pd/Si ratio makes this material more attractive for catalytic and hydrogen storage applications.

Cette thèse s’inscrit dans le cadre d’un projet GREENANONANO né d’un partenariat entre le Luxembourg Institute of Science and Technology (LIST), Goodyear et l’Université de Lorraine dans le but de relever un défi technologique concernant l’augmentation des performances des propriétés viscoélastiques de la gomme utilisée dans les pneumatiques. Cette gomme est un composite constitué d’un élastomère (caoutchouc naturel) renforcé par la silice et le noir de carbone. La dispersion de ces charges n’est pas optimale et tend à dégrader les propriétés mécaniques et électrostatiques et donc les performances des pneus. Faces à ces limitations industrielles, l’utilisation d’autres types de renforts tels que les nanotubes de carbone devient une alternative crédible. Etant donné que les nanotubes de carbone (NTCs) ont tendance à s’organiser en fagots, le problème de la dispersion reste à résoudre. Nous proposons dans cette thèse la mise en place d’un matériau biphasé constitué de silice mésoporeuse naturelle, appelée diatomite, sur laquelle ont été synthétisés des NTCs. La grande surface spécifique de la diatomite offre la possibilité d’y faire croître une grande densité de NTCs et d’accroître significativement la surface de contact avec la matrice polymère. Cette thèse multidisciplinaire a débuté par la synthèse de nanoparticules métalliques par ALD pour la croissance de NTCs, suivie d’un développement du procédé de croissance de NTCs sur la diatomite. L’intégration réussie des charges biphasées obtenues au sein de matrices polymériques (élastomère, thermoplastique) a permis de mesurer les propriétés mécaniques, thermiques et électriques des nanocomposites ainsi fabriqués / This thesis is part of the GREENANONANO project ensuing from a partnership between the Luxembourg Institute of Science and Technology (LIST), Goodyear Company and Université de Lorraine, in order to address a technological challenge for increasing tires performances. The latter are directly related to the viscoelastic properties of the rubber used in tires. This gum is a composite material made by mixing an elastomeric matrix (natural rubber) and fillers (silica and carbon black). Nowadays, the filler dispersion is not optimal, which degrades the mechanical and electrostatic properties and therefore performances of tires. All these industrial limitations require the use of other types of reinforcing agents such as carbon nanotubes. Since carbon nanotubes tend to be organized into bundles, the dispersion problem still exists. We therefore propose in this thesis the synthesis of a biphased material composed by diatomite particles (natural mesoporous silica) on which are grown carbon nanotubes (CNTs). The high surface area of diatomite offers the possibility of growing a high density of CNTs, increasing the contact area with the polymer matrix. This multidisciplinary thesis started with the synthesis of metal nanoparticles by Atomic Layer Deposition (ALD) to catalyse the growth of CNTs and then a process was developed to grow CNTs on diatomite particles. The successful integration of the resulting biphased particles in polymer matrices (elastomer, thermoplastic) allowed to measure the mechanical, thermal and electrical properties of the nanocomposites thus produced

Orientadores: Cecília Amélia de Carvalho Zavaglia, Carmen Gilda Barroso Tavares Dias / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T18:23:16Z (GMT). No. of bitstreams: 1 Andrade_SabinadaMemoriaCardosode_D.pdf: 7127568 bytes, checksum: 0ebd83d085ffff7fe81cf8749ab309fb (MD5) Previous issue date: 2012 / Resumo: A coesão de um grupo de profissionais de diversas áreas onde haverá troca de informações para a concretização de um biomaterial é fator decisivo para reunir todos os requisitos necessários de caracterizações físicas, químicas e biológicas e assim garantir biocompatibilidade e biofuncionalidade, associadas à interação entre o tecido vivo e o biomaterial. Scaffold biodegradável que combina a bioatividade de hidroxiapatita (HA) e a degradabilidade ajustável de matriz de poliuretano (PU) obtido a partir do PVAl foi desenvolvido nesta pesquisa e submetido à caracterizações morfológicas, mecânicas e biológicas. Este novo tipo de scaffold não é tóxico, apresenta interconexão de poros e microporos nas paredes dos poros, boa resistência mecânica e boa ativação de crescimento celular, propriedades que satisfazem as exigências do uso clínico. As análises através de microscopia eletrônica de varredura mostram além da conexão de poros as nanopartículas de hidroxiapatita distribuídas de maneira uniforme na matriz do bionanocompósito. Os valores médios de resistêcia à compressão da matriz e do bionanocompósito foram próximos de 60 MPa tanto para PVAl-PU como para PVAl-PU/HA com 25% de HA, e 105 MPa PVAl-PU/HA com 33% de HA. Após 24 horas de implante o biomaterial PVAl-PU/HA já apresentou em observação por MEV, detalhe de células aderidas, sugestivas provavelmente de células de fibroblasto, espraiamento com formação de uma camada celular compacta e homogênea e após 14 dias do implante foi observada a interação do biomaterial com as camadas do tecido subcutâneo e a invasão do crescimento celular pelos poros interconectados do scaffold. Portanto o scaffold desenvolvido neste trabalho é indicado com expectativas promissoras para implantes ósseos / Abstract: The cohesion of a group of professionals from many areas, exchanging information to concretize a bio material, is a crucial factor to gather all of the requirements of physical, chemical, and biological characterization and therefore ensure biocompatibility and bio functionality, associated to the interaction of the living tissue and the biomaterial. In this research it was developed and subjected to morphological, mechanical and biological characterization, a biodegradable scaffold that combines the bioactivity of hydroxyapatite (HA) and the adjustable degradability of polyurethane matrix (PU) obtained from the PVA1. This new kind of Scaffold is non toxic, has interconnected pores and micropores at the pore's wall, great mechanical resistance and great cellular growing activation. These properties meet the clinical use requirements. The scanning electronic microscopy analysis shows, beside the pore connection, the hydroxyapatite microparticles arranged evenly in the bionanocomposite. The medium values of compression resistance of the matrix and of the bionanocomposite were close to 60 MPa for PVA1-PU well as PVA1-PU/HA with 25% of HA, and 105 MPa PVA1-PUH/HA with 33% of HA. After 24 hours of insertion, the biomaterial PVA1-PU/HA presented as seen in MEV observation, adherent cells, probably coming from fibroblast cells, spreading with a cellular compact and homogeneous layer and, after 14 days of the insertion, it was observed the biomaterial interaction with the layers of the subcutaneous tissue and the invasion of the cellular growing through the scaffold's interconnected pores. Therefore, the osseous scaffold is indicated with promissing expectations to implants / Doutorado / Materiais e Processos de Fabricação / Doutora em Engenharia Mecânica

To develop a hydrogel sensor system using the Hall effect to detect the degree of swelling, gels containing high concentrations of magnetic particles are necessary to induce a strong magnetic field. For this purpose, hydrogels based on poly(N-isopropylacrylamide) cross-linked with Laponite XLS are modified with various magnetic nanoparticles. The focus of this work is to introduce high particle densities with a homogeneous distribution into the gel. Particles are coated with 3-(trimethoxysilyl)propyl methacrylate to bind them into the network structure. The swelling behavior and temperature response of gels containing pure and modified particles are compared to the unmodified clay gel. Ferrogels are further synthesized in a magnetic field to permanently align magnetic nanoparticles in the network. This results in permanently embedded rod-like structures spanning the entire length of the gel. The influence of this anisotropic distribution on the mechanical properties of the hydrogel is investigated through compression measurements.

Hydrogen is considered as an alternative clean energy source due to the depletion of fossil fuels and related environmental problems. Steam reforming of bio-ethanol, has excellent potential for hydrogen production, with CO2 neutrality. Ni, Pd and Pt are the most active metals for steam reforming of ethanol. Improving catalytic activity of supported Ni catalyst by incorporating small amount of Pd or Pt is a successful method for increasing activity and stability of the catalyst. Development of active and stable catalysts with low coke formation and high hydrogen yield attracted major attention of researchers in recent decades. MCM-41 supported bimetallic mesoporous catalytic materials containing well dispersed Ni and Pd nanoballs were synthesized following an impregnation procedure. TEM images and XRD analysis of these materials indicated the formation of nickel and palladium nanoballs of 15-25 nm and 5-8 nm respectively, within the synthesized materials. These materials have quite narrow pore-size distributions in the range of 1-5 nm. In the calcined materials, nickel was in Ni+3 and Ni+2 states, however in the reduced sample most of the nickel was in Nio state, together with some NiO. Formation of NiOx crystals takes place after the calcination step. Impregnation of palladium into Ni/MCM-41 caused a decrease in the reduction temperature of NiO for about 50oC. Activity of the catalytic materials were tested in the reaction of steam reforming of ethanol.all the catalysts showed high conversion and quite high hydrogen yield over 400 oC. PdNi impregnated MCM-41 supported catalysts showed higher conversion of ethanol but lower hydrogen yield than Ni impregnated catalysts due to methane formation in the case of Pd incorporation. However, MCM-41 does not show enough hydrothermal stability for steam reforming of ethanol reaction. SBA-15 has very similar physical properties of MCM-41 with larger pores and high hydrothermal stability. Ceria also has widespread applications in catalysis area with its excellent oxygen buffering capacity. It can be used as catalyst support and also an improving agent for silica supports. Mesoporous silica SBA-15 with ordered pore structure was synthesized following a hydrothermal procedure and then bimetallic Ni-Ce and Pd-Ni-Ce incorporated mesoporous silica catalysts were prepared and tested in steam reforming of ethanol. On the other hand, ceria enriched silica structures i.e cerium/silicate composites were also synthesized. However the syntheses were unsuccessful due to the thermal sintering of ceria. Addition of ceria to the support structure decreased coke formation significantly.. According to the thermal gravimetric analysis studies conducted after ethanol steam reformin reaction at 600 oC, coke formation with Ni-SBA-15 (Ni/Si=0.10) catalyst was 40% and it was 10% with NiCe-SBA-15 (Ni/Si=0.10, Ce/Si=0.50) Activity test results obtained with Ni incorporated silica catalysts in steam reforming of ethanol gave high hydrogen yield over 4 (max. 6) and complete conversion of ethanol at 600 oC. SBA-15 found to be more stable catalyst than MCM-41 in the steam reforming of ethanol reaction. The highest hydrogen yield values were achieved by AlMCM-41 supported Ni-Ce impregnated catalysts. Aluminum in the slica matrix (3% wt.) increased the catalytic activity significantly, by giving acidic properties to the catalyst. Simultaneous and consecutive Ni and Ce impregnation were also examined. AlMCM-41 supported, consecutively Ce and Ni impregnated catalysts with Ce/Si and Ni.Si molar ratio sof 0.10, showed very high catalytic activity (5.8 at the beginning). AlMCM-41 supported catalyst were less stable because of high activity and consequently coke formation.

Le travail de thèse présenté dans ce manuscrit s’inscrit dans une dynamique d’intégration de matériaux non conventionnels en systèmes microfluidiques. Il vise à démontrer le potentiel du cPDMS, un matériau nanocomposite formé d’une matrice de polydiméthylsiloxane rendu conducteur par l’ajout de nanoparticules de carbone. Compatible avec les procédés technologiques habituels, le cPDMS peut être structuré dans une large gamme d’épaisseurs et de géométries mais présente surtout l’avantage de pouvoir être collé irréversiblement sur verre, PDMS et silicium. Son intégration est parfaitement étanche, rapide à mettre en oeuvre, et très économique. La première partie du manuscrit est consacrée à la caractérisation de ce matériau. Ses propriétés électriques et de surface, pouvant être critiques pour une utilisation en microfluidique, ont été particulièrement étudiées. Les champs électriques offrant de nombreuses possibilités pour réaliser des fonctions clés en microfluidique (détection, séparation, manipulation de fluides ou de particules), nous avons choisi d’évaluer l’intérêt d’électrodes de cPDMS dans deux types d’applications. Les aspects de détection ont d’abord été mis en évidence à l’aide de mesures électrochimiques. Cette méthode a permis à la fois de caractériser la surface du cPDMS tout en validant son utilisation potentielle pour des applications d’analyses électrochimiques. Dans la dernière partie du manuscrit, le matériau a été testé pour la manipulation de particules à travers l’observation de différents phénomènes électrocinétiques. Ceux-ci ont conduit à la mise au point de dispositifs microfluidiques (intégrant des lectrodes de cPDMS) dédiés à la lyse et à l’électrofusion de cellules. / The work presented in this thesis deals with the integration of non-conventional materials in microfluidic systems. It aims to demonstrate the potential of cPDMS, a conductive nanocomposite material made up of polydimethylsiloxane matrix mixed with carbon nanoparticles. Compatible with the usual technological processes such as soft lithography, cPDMS can be microstructured in a large range of thicknesses and geometries. Moreover, cPDMS can be quickly, irreversibly and perfectly sealed to glass, PDMS and silicon substrates, something that is not possible for conventional metallic electrodes. The first part of the manuscript is centered on the characterization of this material. Its electrical and surface properties that may turn out critical for microfluidic applications have been particularly studied. Electric fields present many opportunities to perform key functions in microfluidic (detection, separation, fluid or particles handling). We have chosen to assess the potential of cPDMS electrodes for two kinds of applications. Aspects of detection were first demonstrated using cyclic voltammetry measurements. This electrochemical method has enabled both to characterize the cPDMS surface while validating its potential as an electrochemical analysis tool. In the last part of this manuscript, cPDMS was tested for the electrokinetic manipulation of particles through thre study of different electrical fields with induced phenomena. This has led to the development of microfluidic devices (integrating cPDMS electrodes) designed for cell lysis and cells electrofusion.