In this work, nanocomposite cathode powder and nano/micro-structured composite cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs) have been produced using induction plasma spray. Both the suspension plasma spray (SPS) and solution plasma spray (SolPS) method were used. The composite cathode is a mixture of electronic and ionic conductor (ceramic oxide) with enough porosity for the oxygen gas to pass and have the expansion coefficient compatibility with the electrolyte as well. For the purpose of SOFC commercialization, there is a trend to develop SOFCs working at a medium temperature range (600-800[degrees]C). This not only expands the choice of materials and stack geometries that can be used but also reduces system cost and, in principle, decreases the degradation rate of the stack and system components.In order to reduce the polarization resistance of the cathode at this temperature range, two approaches are proposed for cathode fabrication: a) using the materials both with high ionic and electronic conductivities, such as adding a second phase into the original cathode material; b) producing the cathode with homogeneous nano/micro-structure. SolPS method was used to synthesize nanopowders with mixed conductivity. The solution precursor was prepared with the mixed stoichiometric metal nitrates, glycine and distilled water. The crystallinity and morphological features of the nanopowders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Afterwards, the suspensions, made with ethanol and previously synthesized composite nanopowders were used to deposit cathode coatings by SPS process. The parameters of the SPS processes are optimized to obtain cauliflower microstructure with maximized homogeneity and appropriate open porosity. Cathodes produced by a SPS process were compared to the ones produced using a SolPS process. The coatings were characterized by the high resolution SEM. Symmetrical SPS cathode-electrolyte-cathode was also fabricated to test the polarization resistance of the cathode using electrochemical impedance spectroscopy (EIS). Cathode material nanopowder mixtures of Ce[subscript 0.8]Gd[subscript 0.2]O[subscript 1.9] (GDC) and La[subscript 0.6]Sr[subscript 0.4]Co[subscript 0.2]Fe[subscript 0.8]O[subscript 3] (LSCF6428) with different mass ratio, such as 30wt%:70wt% and 60wt%:40wt% of GDC:LSCF, were obtained. The composite nanopowders exhibit a perovskite structure of LSCF6428 and a fluorite structure of GDC and the two phases are homogeneously dispersed. The nanoparticles are almost globular in shape with a diameter from 10 nm to 60 nm and with BET specific areas around 20 m[superscript 2]/g. Homogeneous cauliflower-structure composite cathodes were obtained by both SPS and SolPS methods. The potentials of these two deposition technologies to provide functionally graded composite cathode with high homogeneity were demonstrated. Compared to SolPS cathodes, the SPS cathodes have finer nanostructure, higher porosity and better distributed pores, which takes advantage of the homogeneously distributed nanosized powders in the precursors. The SPS coatings were expected to have enlarged triple phase boundaries. Dans ce travail, des poudres nanocomposites contenant des phases mélangées nano et microstructurées de cathodes pour les piles à combustible à température moyenne (IT-SOFCs) ont été produits [sic] en utilisant un plasma thermique inductif. Deux techniques ont été utilisées, soit la déposition en utilisant des suspensions (SPS) ou encore en utilisant des solutions (SolPS ou SPPS ). La cathode composite est un mélange de conducteur électronique et de conducteur ionique (oxyde céramique) avec assez de porosité pour que l'oxygène passe et aussi pour assurer la compatibilité des coefficients d'expansion avec l'électrolyte. Afin de permettre la commercialisation des SOFCs, le développement des SOFCs s'oriente vers des piles fonctionnant à une température ambiante moyenne (600-800[degrés]C). Ceci augmente le choix des matériaux et des géometries de pile qui peuvent être employés, réduisant les coûts et, en principe, devrait aussi diminuer le taux de dégradation des composants des piles et des systèmes. Afin de réduire la résistance de polarisation de la cathode à cette gamme de température, on propose deux approches pour la fabrication de la cathode : a) en utilisant les matériaux avec des conductivités ioniques et électroniques élevées, qui peuvent être obtenus en ajoutant une deuxième phase dans la cathode ; b) la synthèse de cathodes avec des morphologies optimisées de nano/microstructure. La méthode SolPS a été employée pour synthétiser des nanopoudres possédant une conductivité mixte. Le précurseur de la solution a été préparé avec des nitrates, la glycine et l'eau distillée stoechiométriques mélangés en métal. La cristallinité et la morphologie des nanopoudres ont été caractérisées par la diffraction de rayon X (DRX), la microscopie électronique à balayage (MEB), la microscopie électronique à transmission (MET) et la spectroscopie à dispersion d'énergie (EDS). Des suspensions, faites avec de l'éthanol et les nanopoudres composites précédemment synthétisées, ont été employées pour déposer des revêtements de cathode par le procede SPS. Les paramètres des procédés SPS ont été optimisés. Des cathodes nanostructurées produites par le procede SPS ont été comparées à celles produites en utilisant le procédé SolPS. Les revêtements ont été caracterisés par un MEB à haute résolution. Des cathode-électrolyte-cathode symétriques ont également été fabriquées pour examiner la résistance de polarisation de la cathode en utilisant la spectroscopie électrochimique d'impédance (EIS). Des mélanges de nanopoudres de cathode de Ce0.8Gd0.201.9 (GDC) et de La0.6Sr0.4Co0.2Fe0.803 (LSCF6428) avec les ratios massiques suivants : 30 - 70 et 60 - 40 % masse de GDC - LSCF, ont été obtenus. Les nanopoudres composites montrent une structure de pérovskite de LSCF6428 et une structure de fluorite de GDC et ces deux phases sont homogènement dispersées. Les nanoparticles [sic] sont presque globulaires avec un diamètre de 10 à 60 nanomètre et avec des surfaces spécifiques autour de 20 m[indice supérieur 2]/g. Des cathodes composites de structure homogène en forme de choux fleur [sic] ont été obtenues par les méthodes de SPS et de SolPS. Les potentiels de ces deux technologies de depôt pour fournir des cathodes composites fonctionnelles à composition gradée et avec une homogénéité élevée ont été démontrés. Comparé aux cathodes produites par SolPS, les cathodes produites par SPS ont une nanostructure plus fine, une porosite élevée et des pores mieux distribués.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: In materials chemistry, surface-initiated reversible deactivation radical polymerisation (SI-RDRP) has emerged as one of the most versatile routes to synthesising inorganic/organic hybrid materials consisting of well-defined polymers. The resultant materials often exhibit a remarkable improvement in bulk material properties even after the addition of very small amounts of inorganic modifiers like clay. A novel cationic reversible addition–fragmentation chain transfer (RAFT) agent with the dual purpose of modifying the surface of Laponite clay and controlling the polymerisation of monomer therefrom, was designed and synthesised. Its efficiency to control the polymerisation of styrene was evaluated and confirmed through investigating the molar mass evolution and chain-end functionality. The surface of Laponite clay was modified with the cationic chain transfer agent (CTA) via ion exchange and polymerisation performed in the presence of a free non-functionalised CTA. The addition of the non-functionalised CTA gave an evenly distributed CTA concentration and allowed the simultaneous growth of surface-attached and free polystyrene (PS). Further analysis of the free and grafted PS using analytical techniques developed and published during the course of this study, indicated that the free and grafted PS chains were undergoing different polymerisation mechanisms. For the second monomer system investigated n-butyl acrylate, it was apparent that the molar mass targeted and the monomer conversions attained had a significant influence on the simultaneous growth of the free and grafted polymer chains. Additional analysis of the grafted polymer chains indicated that secondary reactions dominated in the polymerisation of the surface-attached polymer chains. A new approach to separating the inorganic/organic hybrid materials into their various components using asymmetrical flow field-flow fractionation (AF4) was described. The results obtained not only gave an indication of the success of the in situ polymerisation reaction, but also provided information on the morphology of the material. Thermogravimetric analysis (TGA) was carried out on the polymer-clay nanocomposite samples. The results showed that by adding as little as 3 wt-% of clay to the polymer matrix, there was a remarkable improvement in the thermal stability. / AFRIKAANSE OPSOMMING: Oppervlakgeïnisieerde omkeerbare deaktiveringsradikaalpolimerisasie (SI-RDRP) is een van die veelsydigste roetes om anorganiese/organiese hibriedmateriale (wat bestaan uit goed-gedefinieerde polimere) te sintetiseer. Die produk toon dikwels ʼn merkwaardige verbetering in die makroskopiese eienskappe – selfs na die toevoeging van klein hoeveelhede anorganiese modifiseerders soos klei. ʼn Nuwe kationiese omkeerbare addisie-fragmentasie kettingoordrag (RAFT) middel met die tweeledige doel om die modifisering van die oppervlak van Laponite klei en die beheer van die polimerisasie van die monomeer daarvan, is ontwerp en gesintetiseer. Die klei se doeltreffendheid om die polimerisasie van stireen te beheer is geëvalueer en bevestig deur die molêre massa en die funksionele groepe aan die einde van die ketting te ondersoek. Die oppervlak van Laponite klei is gemodifiseer met die kationiese kettingoordragmiddel (CTA) deur middel van ioonuitruiling en polimerisasie wat uitgevoer word in die teenwoordigheid van ʼn vrye nie-gefunksionaliseerde CTA. Die toevoeging van die nie-gefunksionaliseerde CTA het ʼn eweredig-verspreide konsentrasie CTA teweeggebring en die gelyktydige groei van oppervlak-gebonde en vry polistireen (PS) toegelaat. Verdere ontleding van die vrye- en geënte PS met behulp van analitiese tegnieke wat ontwikkel en gepubliseer is gedurende die verloop van hierdie studie, het aangedui dat die vry- en geënte PS-kettings verskillende polimerisasiemeganismes ondergaan. n-Butielakrilaat is in die tweede monomeer-stelsel ondersoek en dit was duidelik dat die molêre massa wat geteiken is en die geënte polimeerkettings. ʼn Nuwe benadering tot die skeiding van die anorganiese/organiese hibriedmateriale in hulle onderskeie komponente met behulp van asimmetriese vloeiveld-vloei fraksionering (AF4) is beskryf. Die resultate wat verkry is, het nie net 'n aanduiding gegee van die sukses van die in-situ polimerisasiereaksie nie, maar het ook inligting verskaf oor die morfologie van die materiaal. Termogravimetriese analise (TGA) is uitgevoer op die polimeer-klei nanosaamgestelde monsters. Die resultate het getoon dat daar 'n merkwaardige verbetering in die termiese stabiliteit was na die toevoeging van so min as 3 wt% klei by die polimeermatriks.

The scope of this work is to fathom different possibilities to create functional coatings with polymer brushes. The immobilization of nanoparticles and enzymes is investigated, as well as the affection of their properties by the stimuli-responsiveness of the brushes. Another aspect is the coating of 3D-nanostructures by polymer brushes and the investigation of the resulting functional properties of the hybrid material. The polymer brush coatings are characterized by a variety of microscopic and spectroscopic techniques, with a special emphasis on the establishment of the combinatorial quartz crystal microbalance/spectroscopic ellipsometry technique as a tool to characterize the functional properties of the polymer brush systems insitu. The pH-responsive swelling of the polyelectrolyte brushes poly(acrylic acid) and poly(2-vinylpyridine), as well as the thermoresponsive swelling of poly(N-isopropylacryl amide) is studied in detail by this technique. Poly(2-vinylpyridine) and binary poly(N-isopropylacryl amide)-poly (2-vinylpyridine) brushes are used as templates for the insitu-synthesis of palladium and platinum nanoparticles with catalytic activity. As an example for the use of polymer brushes to immobilize enzymes, the model enzyme glucose oxidase is physically adsorbed to poly (2-vinylpyridine) and poly (acrylic acid) brushes and also covalently bound to poly (acrylic acid) brushes. In the last part of this thesis, sculptured thin films are coated with poly (acrylic acid) and poly (N-isopropylacryl amide) brushes and the swelling characteristics as well as the adsorption behavior of the model protein bovine serum albumin are investigated.

<p>Poli(mlečna kiselina) (PLA) predstavlja jedan od najpopularnijih komercijalnih biorazgradivih polimera. Iako može da zameni neke od najče&scaron;će kori&scaron;ćenih sintetskih polimera, neka njegova svojstva (lo&scaron;a barijerna, termička i mehanička) jo&scaron; uvek predstavljaju prepreku u &scaron;iroj primeni, posebno za pakovanje hrane. Jedan od najsavremenijih načina prevazilaženja nedostataka u svojstvima biopolimera predstavljaju nanotehnologije.<br />U ovom radu ispitan je uticaj dodatka različitih koncentracija hidrofobnih nanočestica silicijum (IV) oksida (od 0.2 mas.% do 5 mas.%) pripremom uzoraka u rastvoru, i rastopu na toplotna, mehanička, i barijerna svojstva PLA. Morfolo&scaron;ke karakteristike uzoraka nanokompozita snimljene su pomoću skenirajuće elektronske mikroskopije (SEM). Ostvarena je izuzetno dobra disperzija i distribucija hidrofobnih čestica silicijum (IV) oksida koje su u malim udelima dodavane u poli(mlečnu kiselinu). Dobra disperzija i distribucija hidrofobnih čestica silicijum (IV) oksida ostvarena je kako pripremom nanokompozita metodom u rastvoru, tako i metodom u rastopu.<br />Toplotna svojstva PLA i pripremljenih nanokompozita proučavana su primenom diferencijalnog skenirajućeg kalorimetra (DSC), dok je stepen kristalnosti određen rasipanjem X zraka pod &scaron;irokim uglom(WAXD). Mehanička svojstva su ispitivana da bi se odredio uticaj dodatka nanočestica SiO2 na prekidnu čvrstoću i izduženje čistog PLA. Iako su prilikom pripreme materijala metodom u rastvoru, pobolj&scaron;anja mehaničkih i barijernih svojstava postignuta pri udelima silicijum (IV) oksida u rasponu od 0,2 do 5 mas.%, najznačajnija pobolj&scaron;anja postignuta su za najmanje udele nanočestica (0,2 mas.% i 0,5 mas.%). Pobolj&scaron;anja mehaničkih i barijernih svojstava nanokompozita, primenjenih metodom u rastopu, su registrovana i za udele silicijum (IV) oksida od 0,2 do 3 mas.%.<br />Takođe je ispitana mogućnost primene pripremljenog nanokompozita na osnovu poli(mlečne kiseline) i silicijum (IV) oksida za pakovanje prehrambenih proizvoda na primeru pakovanja svežeg svinjskog mesa (M. longissimus thoracis et lumborum). Ispitivanjem uticaja materijala za pakovanje svežeg mesa u vakuumu, na parametre tehnolo&scaron;kog (pH, boja), senzorskog, i mikrobiolo&scaron;kog kvaliteta mesa, utvrđeno je da su PLA kao i nanokompoziti na osnovu PLA sa različitim udelima silicijum (IV) oksida, pogodni za vakuum pakovanje i skladi&scaron;tenje svežeg svinjskog mesa.</p> / <p>Poly(lactic acid) presents one of the most popular bio-polymers for diverse applications. However, the use of PLA as food packaging material is limited due to poor barrier and mechanical properties. These properties could be improved by incorporation of nanoparticles into polymer matrix.<br />In this work neat PLA films and PLA films with different percentage of hydrophobic fumed silica nanoparticles (0,2 wt.% to 5 wt.%) were prepared by solution casting and melt blending methods. Several procedures were used to characterize the influence of different silica content on dispersion (SEM), crystalline behavior (WAXD), thermal stability (DSC, TGA), mechanical and barrier properties. It is shown that the applied techniques and selection of specific hydrophobic spherical nanofiller provide a good dispersion and distribution of silica nanoparticles in poly(lactic acid) for both film preparation methods.<br />Characteristics of films prepared by solution casting method showed improvements in mechanical and barrier properties for all loadings of nanofiller but the most significant improvements were achieved for lowest silica content (0,2 wt.% and 0,5 wt.%) The improvements in material characteristics (mechanical and barrier) for melt blending method were also achieved (for concentrations from 0,2 wt.% to 3 wt.%).<br />After film preparation, selected cuts of M. longissimus thoracis et lumborum were packed in prepred films of polymer nanocomposites, and the shelf-life characterisation was conducted on technological, sensory and microbiological paramethers of quality. After shelf-life characterisation it can be concluded that polymer nanocomposites based on PLA and silica nanoparticles could be used for packaging od fresh pork meat in vacuum.</p>

Ce travail concerne l'étude du comportement rhéologique de nanocomposites modèles à base de Laponite dans du polyoxyde d'éthylène ou des mélanges polyoxyde d'éthylène avec du polyméthacrylate de méthyle. L'influence des paramètres moléculaires, masse molaire de la matrice et mode de protection des particules sur les propriétés rhéologiques a été étudiée. La meilleure dispersion est obtenue à partir d'une solution, la dilution d'un mélange maître conduisant à des matériaux hétérogènes. Les mélanges POE/PMMA sont compatibles à l'état fondu dans toute la gamme de concentrations mais hétérogènes à température ambiante au-dessus de 30% en poids de particules. En diluant un mélange Laponite/PEO dans le PMMA, nous avons montré que ces domaines se concentrent en particules en dessous de 30% de PEO et qu'une cocontinuité de phases PEO contenant les particules et PMMA essentiellement pur est formée au-dessus de 30% de PEO. La présence des particules diminue fortement la cristallinité. / This study concerns model nanocomposites based on Laponite and polyethylene oxide, alone or blended with polymethylmethacrylate. We studied the influence of the parameters on rheological properties of model PEO/Laponite nanocomposites such as matrix molecular weight, preparation method. The best dispersion state of the particles is obtained from solution. Melt dispersion leads to a low frequency modulus which depends on the length and grafting density of the particles. Heterogeneous materials are obtained from melt dispersion of a master batch. PMMA/PEO blends appear to be homogeneous at room temperature only for PEO concentration less than 30wt%. Laponite particles are concentrated in small domains where most of PEO has been extracted. At higher concentrations of PEO, a continuous phase containing PEO and Laponite above percolation concentration is observed, leading to an elastic modulus at low frequency. The presence of Laponite decreases significantly the crystallinity of PEO.

Mimicking nature gives rise to many important facets of biomaterials. This study is inspired by nature and reports on the fabrication of an intercalated polymer-NiTi nanocomposite that mimics the structural order of urethral tissue performing micturition. PTFE is chosen due to its hydrophobicity, low surface energy, and thermal and chemical stability. NiTi has been selected as a prime candidate for this research due to its excellent mechanical stability, corrosion resistance, energy absorbance, shape memory and biocompatibility. Nanoscale engineering of intercalated nanocomposites is done by PVD sputtering PTFE and NiTi. FTIR spectroscopy confirms that PTFE reforms as polymer chains after sputtering. Suitable PVD sputtering parameters were selected by investigating their influence on deposition rates, microstructure and properties of PTFE and NiTi thin films. PTFE forms stable nanocomposite coatings with NiTi and displays favourable surface interactions, known as ‘intercalation’. Intercalated PTFE-NiTi films were fabricated as layered and co-sputtered thin films. Co-sputtered nanocomposites contained nearly one-third vacant sites within its internal microstructure because of intercalation while intercalation introduced minute pits in fibrous NiTi columns of layered nanocomposites. These pits allow PTFE to extend their chains and crosslinks, resulting in microstructural and functional changes in the thin films. Intercalated PTFE-NiTi nanocomposites offer a close match to the natural tissue in terms of responding to the fluid contact (wetting angle modifications), and allow the soft and hard matter to incorporate in one framework without any chemical reactions (intercalation). An intercalated microstructure in co-sputtered and layered nanocomposites was verified by EDS-SEM and EDS-TEM techniques. The functional responses were witnessed by changes in water contact angle (WCA) and coefficient of friction (CoF) values measured on the film surface. The WCA (99°) and CoF (0.1 – 0.2) of the intercalated nanocomposite (sample PNT12) were different to the NiTi (top layer). WCA and CoF indicate the internal microstructural interactions because of intercalation. Although the pseudoelastic behaviour of NiTi can provide additional fluid response but the difficulty is an absence of crystallinity in as-deposited NiTi, and the heat treatment that melts PTFE. However, DSC and XRD techniques were employed to find the optimum NiTi composition and transition temperatures for phase transformation related to pseudoelasticity. This study provides the basis to incorporate the shape memory (pseudoelasticity or thermal shape memory effect (shape memory effect)) features of NiTi into the intercalated nanocomposite in future. The intercalated PTFE-NiTi nanocomposite reveals a fascinating research precinct, having the response generating characteristics similar to that of natural tissue.

Recent research demonstrated that polymer based nanocomposites (PNCs) have been engineered in order to improve the arc interruption capability of the circuit breakers. PNCs are the combination of nano-sized inorganic nanoparticles (NPs) and polymers, opened up new developments in materials science and engineering applications. Inorganic NPs are selected based on their physical and chemical properties which could make multifunctional PNCs in order to interrupt the electrical arcs effectively. In particular, we presented the PNCs fabricated by using CuO, Fe3O4, ZnO and Au NPs in a poly (methyl methacrylate) (PMMA) matrix via in-situ polymerization method, recently developed method to avoid NPs agglomeration, leading to good spatial distribution in the polymer matrix. Thus, several samples with various wt% of NPs in PMMA matrix have been fabricated. These PNCs have been characterized in detail for the morphology of NPs, interaction between NPs and polymer matrix, and radiative/thermal energy absorption properties. In the next stage, PNCs are tested to determine their arc interruption performance and impact on the electrical arcs of current 1.6 kA generated using a specially designed test set-up. When PNCs interact with the electrical arcs, they generate ablation of chemical species towards core of the electrical arc, resulting in cooling-down the arc due to strong temperature and pressure gradient in the arc quenching domain. This thesis demonstrates for the first time that these engineered PNCs are easily processed, reproducible, and can be used to improve the arc interruption process in electrical switching applications. / Ny forskning har visat att polymerbaserade nanokompositer (PNCs) har utformats för att förbättra strömbrytares förmåga att undvika ljusbågar vid överslag. PNCs är en kombination av nanostora oorganiska nanopartiklar (NP) och polymerer, som har öppnat upp för ny utveckling inom materialvetenskap och tekniska tillämpningar. Oorganiska NP väljs baserat på deras fysikaliska och kemiska egenskaper som kan hjälpa PNCs att motverka elektriska ljusbågar effektivt. I synnerhet, presenterade vi PNCs tillverkade genom användning av CuO, Fe3O4, ZnO och Au NP i en poly (metylmetakrylat) (PMMA)-matris via in situ-polymerisationsmetod, nyligen utvecklad för att undvika NP-agglomerering, vilket leder till god rumslig fördelning i polymermatrisen. Därför har flera prover med olika vikt% av NP i PMMA-matris tillverkats. Dessa PNCs har utvärderats i detalj för NP-morfologi, interaktion mellan NP och polymermatris, och strålnings- och värmeenergiabsorption. I nästa skede testas PNCs för att bestämma deras förmåga att undvika ljusbågar och påverkan på de elektriska ljusbågarna av 1,6 kA strömstyrka, genererade med hjälp av en specialdesignad test-set-up. När PNCs interagerar med de elektriska ljusbågarna, genererar de ablation av kemiska ämnen mot kärnan i den elektriska ljusbågen, vilket resulterar i nedkylning av ljusbågen på grund av starka temperatur- och tryckgradienter i området. Denna avhandling visar för första gången att dessa konstruerade PNCs är lätta att framställa, reproducerbara, och kan användas för att förbättra avbrottsprocessen för ljusbågen i elektriska kopplingstillämpningar. / <p>QC 20170303</p>

[pt] Nanocompósitos de cobre com nanotubos de carbono (Cu-CNT) são considerados promissores para aplicações em materiais eletrônicos, trocadores de calor e como elementos estruturais. Espera-se que com a adição de CNTs, a matriz de cobre possa melhorar as propriedades mecânicas e de transporte. No presente estudo foram produzidos materiais nanocompósitos de matriz de cobre reforçados 0,5, 2 e 5,0 por cento em massa de MWCNT. O procedimento parte da funcionalização dos MWCNTS por método de oxidação convencional e microondas, e sua posterior incorporação na solução de nitrato de cobre, dispersão, dissociação e redução in-situ, com atmosfera de hidrogênio. Foram avaliadas soluções dispersantes como a água e THF no processo da síntese. Técnicas de compactação a frio com posterior sinterização convencional e Spark Plasma Sintering (SPS) foram usadas para produção de pastilhas. Os CNTs funcionalizados pelo método convencional se mostram efetivos para dispersão e decoração quando utilizado THF como solução dispersante. Análises por TEMEELS indicam a presença de cobre metálico na interface Cu-MWCNT. As pastilhas produzidas por sinterização convencional apresentaram tamanho de grão entre 50 nm e 4 um, com boa distribuição dos CNTs, assim como uma diminuição na resistividade elétrica em 98 por cento usando 5wt por cento MWCNT. Por outro lado, as pastilhas produzidas por SPS apresentaram tamanho de grão entre 50nm e 2 um, com alta segregação e modificação dos MWCNTs nos contornos de grão da matriz, assim como o aumento na resistividade elétrica. Aumento de 139 por cento na dureza e 65.5 por cento no módulo de elasticidade foi observado na amostra contendo 0.5 wt por cento MWCNTs produzida por SPS, enquanto valores similares ou inferiores foram observados nas outras frações em massa de MWCNTs. / [en] Copper- multiwall carbon nanotube nanocomposites (Cu-MWCNT) are been considered as a promising material for applications in electronic materials, heat exchanger and structural elements. It is expected that MWCNT addition in a copper matrix can improve the mechanical and transport properties. In this work Cu matrix nanocomposites reinforced with 0,5 wt percent; 2 wt percent; and 5,0 wt percent MWCNT were produced. The procedure starts from the MWCNTs functionalization by conventional oxidation and microwave methods and subsequent incorporation into the copper nitrate solution, dispersion, dissociation, and in-situ reduction in hydrogen atmosphere. Also, it was evaluated water and THF solutions for MWCNTs dispersants. Cold compaction follow by conventional sintering and Spark Plasma Sintering (SPS) techniques were used to produce pellets. CNTs functionalized by conventional method are shown effective for dispersing and decorating CNTs when THF was used as dispersant solution. TEM-EELS analyses indicate the presence of metallic copper in the Cu- MWCNT interface. Pellets produced by conventional sintering were in the 50nm - 4 um grain size, with good CNT distribution and decreasing in 98 per cent the electrical resistivity using 5wt percent MWCNT. Meanwhile, pellets produced by SPS were in the 50nm - 2um grain size with high segregation and modification of MWCNTs at the grain boundaries, as well as the increase in electrical resistivity. Increase of hardness 139 percent and 65.5 percent in elastic modulus were observed in the sample containing 0.5 wt percent MWCNTs produced by SPS, while similar or lower values were observed in the other MWCNTs fractions.

Esta tese focaliza o desenvolvimento de sistemas nanoestruturados através da intercalação de espécies moleculares e supramoleculares em matrizes lamelares de xerogel de pentóxido de vanádio, visando sua utilização como interfaces em dispositivos sensoriais. Nela se explora principalmente as características dos sistemas supramoleculares, dando destaque ao fato de estarem intimamente relacionadas com a natureza das espécies neles presentes, bem como com o tipo de interação, organização e disposição das mesmas. Nesse contexto, são descritos trabalhos desenvolvidos com V2O5.H2O, o material base do projeto, em combinação com outros materiais, para gerar compósitos com potenciais aplicações na área de sensores. Nessa linha são apresentados principalmente os resultados obtidos para a intercalação de metaloporfirinas no pentóxido de vanádio. Também foi dedicada especial atenção à 4,5-diamino-2,6-dimercaptopirimidina (DADMcP), como espécie intercalante em matriz de pentóxido de vanádio, motivado pelas suas propriedades eletroquímicas interessantes para aplicações em baterias de alta densidade de carga. / Nanostructured systems based on the intercalation of molecular and supramolecular species into lamellar vanadium pentoxide xerogels are focused on this Thesis. The exciting characteristics of the supramolecular systems which are closely related to the nature, interaction and organization of the chemical species involved, have been exploited aiming their application in sensor devices. Special emphasis has been given to the research dealing with vanadium(V) oxide in combination with many other suitable species for generating composite materials exhibiting potential application for sensing purposes. Along this line, the results obtained from the intercalation of metalloporphyrins into the lamellar vanadium(V) oxide matrix have been discussed in great detail. Another system, consisting of 4,5-diamine-2,6-dimercaptopyrimidine (DADMcP) as the intercalating species in vanadium(V) oxide, has also been investigated, stimulated by its promising use in high charge density batteries.

Este projeto de mestrado teve como objetivo a obtenção de látices híbridos constituídos de poli(acetato de vinila) (PVAc) e argila montmorilonita (MMT). O homopolímero de acetato de vinila foi sintetizado através da técnica de polimerização em emulsão na presença de diferentes tipos de argila, sendo empregada uma argila sódica (Na-MMT) e três argilas modificadas (o-MMT) com diferentes sais quaternários de amônio. Poli(álcool vinílico) (PVOH) foi utilizado como colóide protetor e persulfato de amônio (APS) como iniciador. Foi estudada a melhor condição para incorporação da argila na matriz polimérica, visando a esfoliação desta nanocarga, resultando desta maneira na formação de nanocompósitos com propriedades diferenciadas. A influência da presença das argilas foi avaliada em termos da velocidade de consumo de monômero, a qual foi acompanhada por gravimetria. Os látices foram caracterizados quanto ao diâmetro médio de partícula e polidispersidade pela técnica de espalhamento de luz (LS). O teor de coágulos do látex foi calculado por análise gravimétrica e a viscosidade analisada em um viscosímetro rotacional. Os filmes nanocompósitos foram caracterizados pelas técnicas de análise dinâmico-mecânica (DMA), análise termogravimétrica (TGA) e difração de raios X (DRX). A morfologia das partículas de látex foi avaliada por microscopia eletrônica de transmissão (MET). / The goal of this project was the preparation of hybrids latexes constituted by poly(vinyl acetate) (PVAc) and montmorillonite (MMT) clays. The poly(vinyl acetate) homopolymer was synthesized via emulsion polymerization in the presence of different types of clay, one sodium clay (Na-MMT) and organically modified clays (o-MMT) with different ammonium quaternary salts. Poly(vinyl alcohol) (PVOH) was used as protective colloid and ammonium persulfate (APS) as initiator. It was evaluated the best condition for the incorporation of the clay in the polymeric matrix, looking forward the exfoliation of the nanofiller, resulting in the formation of nanocomposites with new and improved properties. The influence of clay type and loading was evaluated in terms of latex stability and monomer consumption rate. The latexes were characterized in terms of particle size diameter and polydispersity by light scattering (LS) technique. Coagulum content was determined by gravimetric analysis and viscosity was analyzed in a rotational viscometer. Nanocomposite films were characterized by dynamic-mechanical analysis (DMA), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). Latex particles morphology was evaluated by transmission electron microscopy (TEM).