<p>This study reports on the changes in the structural properties of a tungsten-filament when exposed to a methane / hydrogen ambient for different durations at various filament-temperatures.</p>

Films and coatings of carbonaceous nanostructures are employed in nanoelectronics, biotechnology and other fields. The aim of the research was to synthesize multi-walled carbon nanotubes and graphite oxide and fabricate coatings thereof. Consequently, multi-walled carbon nanotubes and their coatings were synthesized by the catalytic chemical vapour deposition method. As-grown carbon nanotubes inevitably contain remains of metal catalyst particles. A method developed in the laboratory using CCl4 was successfully applied to remove the residual catalyst from the batch of synthesized carbon nanotubes. Simultaneously, graphite oxide was synthesized from graphite powder by Hummer's method. Coatings and films of carbonaceous nanostructures were fabricated from carbon nanotubes and graphite oxide aqueous suspensions. The analysis of carbon nanotubes coatings revealed that their morphology depends on synthesis parameters. The surface properties of these coatings depend on the amount and nature of functional groups attached to carbon nanotube walls. The analysis of graphite oxide films indicated that Congo red dye addition leads to more compact structure of the nanocomposites due the interaction between functional groups of these particles. / Unikaliomis savybėmis pasižyminčios anglinės nanostruktūros panaudojamos dangų ir plėvelių gamyboje, kurios pritaikomos nanoelektronikoje, biotechnologijoje ir kitose srityse. Šio darbo tikslas buvo susintetinti daugiasienius anglinius nanovamzdelius ir grafito oksidą, pagaminti ir ištirti jų dangas. Mūsų laboratorijoje daugiasieniai angliniai nanovamzdeliai buvo susintetinti cheminio nusodinimo iš garų fazės metodu. Susintetinto produkto valymui nuo katalizatoriaus priemaišų pirmą kartą buvo panaudoti CCl4 garai. Ištyrus CCl4 garais paveiktą medžiagą buvo pagrįstas šio valymo metodo efektyvumas. Grafito oksidas buvo gautas oksiduojant grafitą Hummers'o metodu. Anglinių nanovamzdelių dangos ant skirtingų pagrindų buvo pagamintos cheminio nusodinimo iš garų fazės metodu bei suformuotos panaudojant medžiagos vandenines suspensijas. Grafito oksido su Kongo raudonojo dažo priedu dangos ir plėvelės buvo pagamintos laboratorijoje sukurtu filtravimo į tirpalą metodu. Anglinių nanovamzdelių ir jų dangų tyrimo rezultatai parodė, kad dangų morfologija priklauso nuo sintezės sąlygų, o paviršiaus savybes nulemia prisijungusių funkcinių grupių pobūdis ir kiekis. Ištyrus grafito oksido plėveles ir dangas buvo nustatyta, kad Kongo raudonojo dažo priedas skatina kompaktiškesnių nanokompozitų susidarymą ir stiprina dangų bei plėvelių patvarumą.

Vertically aligned multi walled carbon nanotube (MWCNT) arrays fabricated by xylene pyrolysis in anodized aluminum oxide (AAO) templates without the use of a catalyst, were integrated into a resistive sensor design. The steady state sensitivities as high as 5% and 10% for 100 ppm of NH3 and NO2 respectively at a flow rate of 750 sccm were observed. A study was undertaken to elucidate (i) the dependence of sensitivity on the thickness of amorphous carbon layers, (ii) the effect of UV light on gas desorption characteristics and (iii) the dependence of room temperature sensitivity on different NH3 and NO2 flow rates. An equivalent circuit model was developed to understand the operation and propose design changes for increased sensitivity. Multi Walled Carbon NanoTubes (MWCNTs) – Polymer composite based hybrid sensors were fabricated and integrated into a resistive sensor design for gas sensing applications. Thin films of MWCNTs were grown onto Si/SiO2 substrates via xylene pyrolysis using chemical vapor deposition technique. Polymers like PEDOT:PSS and Polyaniline (PANI) mixed with various solvents like DMSO, DMF, 2-Propanol and Ethylene Glycol were used to synthesize the composite films. These sensors exhibited excellent response and selectivity at room temperature when exposed to low concentrations (100ppm) of gases like NH3 and NO2. Effect of various solvents on the sensor response imparting selectivity to CNT – Polymer nanocomposites was investigated extensively. Sensitivities as high as 28% was observed for a MWCNT – PEDOT:PSS composite sensor when exposed to 100ppm of NH3 and -29.8% sensitivity for a MWCNT-PANI composite sensor to 100ppm of NO2. A novel nanostructured electrode design for Li based batteries and electrochemical capacitor applications was developed and tested. High density and highly aligned metal oxide nanowire arrays were fabricated via template assisted electrochemical deposition. Nickel and Molybdenum nanowires fabricated via cathodic deposition process were converted into respective oxides via thermal treatments and were evaluated as electrodes for batteries and capacitor applications via Cyclic Voltammetery (CV). Several chemical baths were formulated for the deposition of pristine molybdenum nanowires. Superior electrochemical performance of metal (Ni and Mo) oxide nanowires was observed in comparison to the previously reported nano-particle based electrodes.

Radio frequency identification (RFID) and sensing are two key technologies enabling the Internet of Things (IoT). Development of RFID tags augmented with sensing capabilities (RFID sensor tags) would allow a variety of new applications, leading to a new paradigm of the IoT. Chipless RFID sensor technology offers a low-cost solution by eliminating the need of an integrated circuit (IC) chip, and is hence highly desired for many applications. On the other hand, printing technologies have revolutionized the world of electronics, enabling cost-effective manufacturing of large-area and flexible electronics. By means of printing technologies, chipless RFID sensor tags could be made flexible and lightweight at a very low cost, lending themselves to the realization of ubiquitous intelligence in the IoT era. This thesis investigated three construction methods of printable chipless RFID humidity sensor tags, with focus on the incorporation of the sensing function. In the first method, wireless sensing based on backscatter modulation was separately realized by loading an antenna with a humidity-sensing resistor. An RFID sensor tag could then be constructed by combining the wireless sensor with a chipless RFID tag. In the second method, a chipless RFID sensor tag was built up by introducing a delay line between the antenna and the resistor. Based on time-domain reflectometry (TDR), the tag encoded ID in the delay time between its structural-mode and antenna-mode scattering pulse, and performed the sensing function by modulating the amplitude of the antenna-mode pulse. In both of the above methods, a resistive-type humidity-sensing material was required. Multi-walled carbon nanotubes (MWCNTs) presented themselves as promising candidate due to their outstanding electrical, structural and mechanical properties. MWCNTs functionalized (f-MWCNTs) by acid treatment demonstrated high sensitivity and fast response to relative humidity (RH), owing to the presence of carboxylic acid groups. The f-MWCNTs also exhibited superior mechanical flexibility, as their resistance and sensitivity remained almost stable under either tensile or compressive stress. Moreover, an inkjet printing process was developed for the f-MWCNTs starting from ink formulation to device fabrication. By applying the f-MWCNTs, a flexible humidity sensor based on backscatter modulation was thereby presented. The operating frequency range of the sensor was significantly enhanced by adjusting the parasitic capacitance in the f-MWCNTs resistor. A fully-printed time-coded chipless RFID humidity sensor tag was also demonstrated. In addition, a multi-parameter sensor based on TDR was proposed.The sensor concept was verified by theoretical analysis and circuit simulation. In the third method, frequency-spectrum signature was utilized considering its advantages such as coding capacity, miniaturization, and immunity to noise. As signal collision problem is inherently challenging in chipless RFID sensor systems, short-range identification and sensing applications are believed to embody the core values of the chipless RFID sensor technology. Therefore a chipless RFID humidity sensor tag based on near-field inductive coupling was proposed. The tag was composed of two planar inductor-capacitor (LC) resonators, one for identification, and the other one for sensing. Moreover, paper was proposed to serve as humidity-sensing substrate for the sensor resonator on accounts of its porous and absorptive features. Both inkjet paper and ordinary packaging paper were studied. A commercial UV-coated packaging paper was proven to be a viable and more robust alternative to expensive inkjet paper as substrate for inkjet-printed metal conductors. The LC resonators printed on paper substrates showed excellent sensitivity and reasonable response time to humidity in terms of resonant frequency. Particularly, the resonator printed on the UV-coated packaging paper exhibited the largest sensitivity from 20% to 70% RH, demonstrating the possibilities of directly printing the sensor tag on traditional packages to realize intelligent packaging at an ultra-low cost. / <p>QC 20150326</p>

Die grundlegende Frage- bzw. Problemstellung der vorliegenden Arbeit war die Entwicklung innovativer Synthesemethoden für die nanoskalige, anorganische Festkörper- und Materialchemie, sowie die umfassende Charakterisierung der neuartigen Materialien und deren Untersuchung hinsichtlich potentieller Anwendungen. Die Arbeit umfasst dabei zwei große Themengebiete: Das Kapitel Bismutbasierte Nanoröhren beschreibt detailliert die neuartige Synthese doppelwandiger Bismut-Nanoröhren (engl. Double Walled Bismuth Nanotubes, DWBiNTs) bei Raumtemperatur, durch die Umsetzung von Bismutmonoiodid mit n-Butyllithium (n-BuLi) zu elementarem Bismut. Elektronenmikroskopische Untersuchungen des resultierenden feinen schwarzen Pulvers zeigen homogen strukturierte, stark agglomerierte, anisotrope Partikel mit Längen von mehreren hundert Nanometer, welche an den Enden geöffnet vorliegen und zudem einen „zwiebelartigen“ Aufbau mit einem einheitlichen inneren Durchmesser von ca. 4,5 nm sowie einen äußeren Durchmesser von ca. 6 nm aufweisen (Abbildung 1 A – C). Auf Grundlage dieser Erkenntnisse wurden von Rasche quantenchemische Rechnungen am Modell einer (34,0)@(40,0)-DWBiNT durchgeführt, aus denen neben einer hexagonal facettierten Querschnittsgeometrie (Abbildung 1 D) durch Rechnungen der elektronischen Eigenschaften eine direkte Bandlücke von 0,5 eV hervorgeht, womit es sich bei diesen Strukturen um Halbleiter handeln sollte. Im Gegensatz zu bislang bekannten Synthesemethoden für Bi-Nanoröhren kann die in der vorliegenden Arbeit entwickelte Syntheseroute als chemische Top-Down-Bottom-Up-Methode verstanden werden. Hiermit soll die Kaskade des Herauslösens der im Festkörper vorgeprägten Strukturen (chemisch Top-Down) gefolgt von deren Reorganisation zu nanoskopischen Objekten (klassisch Bottom-Up) verdeutlicht werden. Diese Herangehens-weise der Niedertemperaturreduktion klassischer Festkörperverbindungen ist bislang einzigartig und konnte basierend auf den Ergebnissen der vorliegenden Arbeit innerhalb des Arbeitskreises bereits erfolgreich auf intermetallische Phasen übertragen werden. Es konnte ferner gezeigt werden, dass es durch die milde Oxidation von DWBiNTs im O2-Strom möglich ist, unter Erhalt der Morphologie gezielt Nanoröhren der unter Normalbedingungen metastabilen β-Modifikation von Bi2O3 zu synthetisieren. Diese wurden in Zusammenarbeit mit dem Kurt-Schwabe-Institut für Mess- und Sensortechnik e.V. Meinsberg hinsichtlich ihrer gassensitiven Eigenschaften untersucht. Während die oxidischen Nanoröhren keine Sensitivität gegenüber CO und nur eine geringe H2-Sensitivität aufweisen, zeigt sich eine signifikante Widerstandserhöhung mit sinkendem Sauerstoffpartialdruck im Gasgemisch. Diese Befunde zeigen eine mögliche, bislang nicht untersuchte Anwendung von Bi2O3 als Sauerstoffsensor. Das Kapitel Mikrowellenunterstützte Niedertemperatursynthese der vorliegenden Arbeit widmet sich – basierend auf dem Polyolprozess (Abbildung 2) – der zeit- und energieeffizienten Synthese der intermetallischen Phasen BiNi, Bi3Ni und BiRh, welche durch herkömmliche metallurgische Hochtemperaturschmelz- oder sinterprozesse nur schwer zugänglich sind. Besonderer Schwerpunkt liegt in der gezielten Synthese mikro- und nanostrukturierter Proben. Die intermetallische Phase Bi3Ni kann röntgenographisch phasenrein in Form homogener stäbchenförmiger Partikel mit Abmessungen von ca. 200 nm x 600 nm, so genanntes submikroskaliges Bi3Ni, synthetisiert werden (Abbildung 3 A). Ebenso erfolgreich gestaltet sich die Synthese der nickelreicheren Phase BiNi in Form von Nadeln mit Durchmessern von wenigen Nanometern und Längen von mehreren Mikrometern sowie der binären Phase BiRh in Gestalt wohl definierter hexagonal facettierter, plättchenartiger Partikel mit einem mittleren Durchmesser von ca. 50 nm und Dicken < 10 nm (Abbildung 3 B, C). In Kooperation mit der Professur Anorganische Chemie I der TU Dresden konnte am Beispiel der intermetallischen Phase Bi3Ni erfolgreich die gezielte Einstellung der Partikelgröße und –morphologie unter Verwendung des mesoporösen Oxids SBA-15 als Exotemplat gezeigt werden. Die herausgelösten Proben zeigen röntgenographisch phasenreine, agglomerierte, sphärische Nanopartikel mit einem Durchmesser von < 8 nm. Die statische Magnetisierung sowie die Transporteigenschaften an den morphologisch unterschiedlichen Proben des Typ-II Supraleiters Bi3Ni wurden in Kooperation mit dem Hochfeld-Magnetlabor des Helmholtz-Zentrum Dresden-Rossendorf untersucht. Es zeigt sich, dass durch chemische Nanostrukturierung physikalische Eigenschaften generiert werden, welche Volumenproben derselben Substanz nicht aufweisen: Die als unvereinbare Antagonisten angesehenen Grundzustände Ferromagnetismus und Supraleitung können in mesoskopischem Bi3Ni nicht nur koexistieren, sondern stärken einander sogar (Abbildung 4). Diese Ergebnisse zeigen beispielhaft, dass Partikelgrößen im Zusammenspiel mit chemischer Substrukturierung in quasi-1D-Bindungssystemen essentiell für das Auftreten neuartiger Quanteneffekte sind. In Zusammenarbeit mit dem Max-Planck-Institut für Chemische Physik fester Stoffe wurden die röntgenographisch phasenreinen Proben von BiNi (Nadeln), Bi3Ni (Stäbchen) und BiRh (hexagonale Nanoplättchen) hinsichtlich ihrer potentiellen Anwendung zur Semihydrierung von Acetylen untersucht. Für die Proben des Systems Bi/Ni kann keinerlei katalytische Aktivität gemessen werden, wohingegen die katalytischen Eigenschaften der BiRh Nanopartikel für die Semihydrierung von Acetylen hervorragend sind. So weisen die hexagonalen Nanoplättchen eine außerordentlich hohe Selektivität gegenüber Acetylen sowie eine sehr gute Langzeitstabilität, im Vergleich zu einem kommerziell erhältlichen Pd/Al2O3 Katalysator, auf. Auf Basis der im Rahmen dieser Arbeit entwickelten und in ihren Ergebnissen (Phase, Reinheit, verschiedene Morphologien) kontrollierbaren sowie zeit- und energieeffizienten reduktiven Solvothermalmethode zur Synthese von intermetallischen Verbindungen ist der Zugang zu weiteren neuartigen, mehrkomponentigen, metallischen Materialien, welche durch klassische metallurgische Hochtemperaturschmelz- oder -sinterprozesse nur schwer oder gar nicht zugänglich sind, möglich. Allgemein kann das beschriebene Verfahren als eine verlässliche, breit anwendbare Methode zur Synthese wohl strukturierter Verbindungen auf chemischem Weg bei Temperaturen bis maximal 250 °C angesehen werden, welches eine große Bandbreite an verschiedenen Einsatzmöglichkeiten bietet.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

abstract: Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface. / Dissertation/Thesis / M.S.Tech Technology 2012

A esbeltez dos perfis de aço formados a frio pode resultar na interação entre diferentes modos de flambagem, tornando a análise desses componentes uma tarefa complexa. Para o projeto de perfis formados a frio, é fundamental a compreensão da natureza do modo de flambagem ao qual estão submetidos. O cálculo de modos de flambagem puros e a quantificação da interação de modos contribuem para o estudo do comportamento desses perfis. Nesse trabalho, o cálculo da carga crítica elástica de modos de flambagem puros ou combinados é realizado através do uso de modelos de elementos finitos restringidos. Para o cálculo focado em uma classe de flambagem específica (de modos globais, distorcionais, locais ou outros), diferentes procedimentos de restrição são propostos. Utilizando um procedimento de restrição geral, o campo de deformações do modelo é restringido de acordo com uma combinação de modos de deformação da seção, definidos com base nos conceitos da teoria generalizada de vigas e do método das faixas finitas restringido. Na direção longitudinal do perfil, podem ser combinados diversos componentes harmônicos que respeitem as condições de contorno das extremidades. Também são mostrados casos em que todos os componentes harmônicos longitudinais possíveis podem ser automaticamente considerados. O cálculo de modos de flambagem combinados possibilita, automaticamente, a quantificação da interação dos modos considerados. Para validação dos procedimentos propostos, são apresentados resultados numéricos da análise de um perfil C com enrijecedores de borda, com duas diferentes condições de contorno das extremidades, e submetidos a dois tipos de carregamento. Os resultados são comparados com os fornecidos pela teoria generalizada de vigas e pelo método das faixas finitas restringido. Os procedimentos de restrição são aplicados na análise de um perfil inspirado em uma estrutura real com apoios intermediários (ao longo do comprimento), explorando a vantagem da implementação utilizando elementos finitos. O potencial dos procedimentos aqui propostos é discutido. Finalmente, foram sugeridos novos objetivos para a continuação desse trabalho. / The slenderness of cold-formed steel member can result in the interaction of different buckling modes, making the analysis of these members a complex task. In the design of thinwalled members, the understanding of the nature of the buckling mode is fundamental. The calculation of pure buckling modes and the evaluation of the interaction amongst the buckling modes help in the study of the behavior of thin-walled members. In this research, the elastic critical buckling load calculation of pure and combined buckling modes is carried out using constrained finite element models. Different constraining procedures are proposed for the calculation focused on each buckling class (of global, distortional, local or other modes). Using a general constraining procedure, the deformation fields of the model are constrained in accordance with a combination of section deformation modes, which are defined based on the concepts of the generalized beam theory and the constrained finite strip method. In the longitudinal direction on the member, several harmonic components may be combined, which must meet the boundary conditions of the member ends. Cases where all possible longitudinal harmonic components can be automatically considered are also presented. In order to validate the proposed procedures, numerical results are presented on the analysis of a lipped channel, with two different configurations of boundary conditions at member ends and submitted to two different types of loading. The results are compared to the ones provided by the generalized beam theory and the constrained finite strip method. The constraining procedures are applied to the analysis of a member inspired by a real structure with intermediate supports (between the member ends), exploring the advantages of the implementation using the finite element method. The potentiality of the procedures proposed herein is discussed. Finally, new aims are proposed in order to continue this research.

Ce travail de thèse expérimental porte sur l'élaboration et l'étude de systèmes hybrides 1D de nanotubes de carbone mono-feuillets, fonctionnalisés de manière non covalente, sous deux aspects. La première étude s'intéresse à l'intercalation de rubidium dans les faisceaux de nanotubes. L'objectif est de faire le lien entre les propriétés structurales des nanotubes dopés et leurs propriétés électroniques au cours du dopage. Un dispositif original dédié, adapté à l'utilisation sur grands instruments et permettant le suivi « in-situ » de l'intercalation par une approche multi-techniques, a été développé dans ce but. Nous mettons en évidence par EXAFS que l'arrangement local autour des ions rubidium est dépendant de la stœchiométrie des composés étudiés. Il apparaît alors qu'à faible taux de dopage, les sites de défauts oxygénés sont privilégiés. Le changement de structure est également relié à une transition semi-conducteur/métal des nanotubes, observée par mesure de résistance électrique et spectroscopie Raman, et induite par le dopage des nanotubes par le rubidium.La seconde partie expérimentale est consacrée à l'étude du confinement d'oligothiophènes à l'intérieur de nanotubes de carbone mono-feuillets. Des mesures de diffraction des rayons X et de microscopie électronique en transmission haute résolution démontrent l'efficacité de notre protocole d'encapsulation. D'autre part, différentes spectroscopies, absorptions UV-Visible et infrarouge et diffusion Raman, indiquent un transfert de charge relativement faible entre les molécules encapsulées et les nanotubes de carbone. Ce résultat est très bien mis en évidence par les modifications de profil, d'intensité et de fréquence des modes Raman hautes fréquences. On notera le bon accord entre les résultats obtenus ici et les effets de renormalisation de l'énergie de phonon discutés dans la littérature. En complément, des effets de confinement liés au diamètre des nanotubes ont été mis en évidence par l'étude des modes Raman basses fréquences. Deux modèles structuraux sont proposés pour expliquer les tendances observées. Le premier suggère un comportement indépendant de la nature de l'espèce insérée. Dans le second, le nombre de chaines d'oligothiophènes encapsulées en fonction du diamètre des tubes est pris en compte. De plus, nous montrons également une influence significative des défauts structuraux sur les systèmes hybrides. / This experimental work concerns the development and the study of 1D hybrid systems of single-walled carbon nanotubes non-covalently fonctionnalized. Two different approaches are discussed. The first experimental study deals with the intercalation of rubidium in carbon nanotubes bundles. The aim is to link structural and electronic properties along the doping process. To do, we developed an original and dedicated home-made set adapted to the use on synchrotron facilities. It permits the following of the intercalation by means of an in-situ multi-techniques approach. In this part, we pointed out that the local environnement of rubidium is dependant of the compound stœchiometries. It appears that oxygenated surface defects are first occupied for low doping rates. The structure modification is also linked to a semiconducting/metal transition of carbon nanotubes observed by resistance measurements and Raman spectroscopy. The second experimental study is devoted to the confinement of oligothiophenes inside single-walled carbon nanotubes. X-Ray diffraction and high resolution transmission electronic microscopy measurements demonstrate the efficiency of our encapsulation process. Several spectroscopic techniques such as UV-Visible and infrared absorptions and Raman diffusion indicate a weak charge transfer between both systems. This result is well evidenced by the profile, intensity and frequency modifications of the high frequency Raman modes. We note the good agreement of these results with the energy renormalisation of phonons discussed in the literature. In addition, some confinement effects depending on carbon nanotubes diameter are pointed out by the study of low frequency Raman modes. Two models are proposed to explain the observed trend. The first one suggests a behavior independent of the nature of the inserted element. In the second one, the number of oligothiophene chains encapsulated in function of carbon nanotubes diameter is considered. We also show a significative influence of carbon nanotube defects on hybrid systems.

Este trabalho traz a aplicação de alta pressão e alta pressão/temperatura (4.0 GPa e 400º C), em amostras de nanotubos de carbono de paredes múltiplas (NTCPM) comerciais para a obtenção de amostras compactas. Os NTCPM foram funcionalizados com ácido nítrico e ácido nítrico/ácido sulfúrico e, também foram usados nanotubos de carbono dopados com nitrogênio. Foram também processadas amostras contendo nanotubos de carbono de paredes múltiplas incorporados em matriz de zircônia obtida pelo método sol-gel. Para aplicação da alta pressão foi usado um sistema com câmaras do tipo toroidal, utilizando grafite como meio transmissor de pressão. Foram obtidas amostras macroscópicas autossuportadas e com resistência ao manuseio principalmente nas amostras de nanotubos de carbono funcionalizados com ácido nítrico/ácido sulfúrico incorporados em zircônia. Para a caracterização das amostras foram utilizadas as técnicas de Microscopia Eletrônica de Transmissão, Espectroscopia Raman, Difração de Raios X e isotermas de adsorção/dessorção de nitrogênio com as quais foi possível determinar que mesmo após a aplicação de alta pressão/temperatura os nanotubos de carbono não sofrem significativas modificações na sua estrutura e nas suas propriedades morfológicas e texturais, confirmando então que os NTCPM mantém suas características originais, apresentando condições para aplicações em dispositivos. As amostras macroscópicas contendo nanotubos de carbono de paredes múltiplas incorporados em zircônia apresentaram ainda resistência à carga de milhares de vezes o seu peso e comportamento de materiais semi-condutores. / This work presents the application of high pressure and/or high pressure/temperature (4.0 GPa and 400 ° C), on different samples of commercial multi-walled carbon nanotube (MWCNT) to obtain compacted samples. MWCNT were functionalized with nitric acid and nitric acid/sulfuric acid, and also carbon nanotubes doped with nitrogen. MWCNT incorporated in a zirconia matrix obtained by sol-gel method were also processed. For high pressure application it was used a system with the toroidal-type chamber, using graphite as a pressure transmitting medium. Self-supported macroscopic samples were obtained, easy to handle, especially in samples of functionalized carbon nanotubes with nitric and sulfuric acid and also incorporated in zirconia. To characterize the samples it was used Transmission Electron Microscopy, Raman Spectroscopy, X-ray diffraction and nitrogen adsoption/desorption isotherms and it was determined that even after application of high pressure/temperature carbon nanotubes do not suffer significant changes in their structure and in their morphological and textural properties, confirming that the CNT keeps its original characteristics and providing conditions for device applications. The macroscopic samples containing MWCNT incorporated in zirconia also exhibited resistance to load of thousands times its own weight and behavior like semiconductor materials.