Orientador: Marcos Akira D' Ávila / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-24T19:12:36Z (GMT). No. of bitstreams: 1 Almeida_RosemeiredosSantos_D.pdf: 3414008 bytes, checksum: 9f5516445d3c90d0f22d3a953197d6b7 (MD5) Previous issue date: 2014 / Resumo: O polímero Poli(caprolactona) (PCL) tem sido amplamente usado como biomaterial nas últimas décadas. Sua biocompatibilidade e boas propriedades termo-mecânicas são as principais características que levam à seleção desse material para aplicação nas áreas biotecnológica, farmacêutica e têxtil. Neste trabalho, montou-se um equipamento para realizar o processamento de eletrofiação e caracterização de mantas formadas por fibras de PCL puro e nanocompósitos de PCL/nanotubos de carbono (NTC). Recorreu-se à eletrofiação com a aplicação de um campo elétrico gerado por uma corrente alternada (CA) e por uma corrente contínua (CC) simultaneamente (CA/CC) visando o controle da estabilidade do escoamento do jato polimérico durante o processamento a fim de determinar os parâmetros de processo e comparar os efeitos das diferentes frequências durante o processamento. Foram obtidos também nanocompósitos de PCL/óxido de grafeno (GO) com aplicação de um potencial elétrico em corrente contínua (CC), a fim de determinar os parâmetros de processos em diferentes concentrações de óxido de grafeno. As soluções/suspensões utilizadas no processo foram caracterizadas através de medições de condutividade elétrica, tensão superficial e propriedades reológicas. As fibras obtidas na forma de mantas porosas não-tecidas (non woven) foram caracterizadas por Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Infravermelho com Transformada de Fourier (FT-IR), Calorimetria Exploratória Diferencial (DSC), Análise Termogravimétrica (TGA), Resistividade, Ângulo de contato ensaios mecânicos de tração e ensaios biológicos in vitro com células tronco mesenquimais humanas (hMSCs). Observou-se que o diâmetro médio das fibras depende da frequência CA aplicada durante a eletrofiação. A análise por FT-IR mostrou que houve a interação entre o PCL e o NTC, e as análises biológicas indicaram que as mantas PCL/GO são promissoras para uso como biomaterial / Abstract: Poly (??caprolactone) (PCL) has been widely used as biomaterial in the last decades. Its biocompatibility and good thermomechanical properties are the main features that lead to the selection of this material for applications in biotechnological, pharmaceutical and textile areas. In this work, an equipment was set up to perform electrospinning; characterization of fibrous mats formed by pure PCL fibers and nanocomposites of PCL/carbon nanotubes (CNT). Electrospinning based on the application of an electric field generated by an alternating current (AC) and a direct current (DC) simultaneously (AC/DC) was performed aiming to control the stability of the jet flow of the polymer during processing in order to determine the process parameters and compare the effects of different frequencies during processing. Nanocomposites of PCL/graphene oxide (GO) with application of a DC electrical potential were also obtained in order to determine the process parameters at different concentrations of graphene oxide. Solutions/suspensions employed in the process were characterized by measurements of electrical conductivity, surface tension and rheological properties. The fibers obtained in the form of non- woven porous mats were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Differential canning Calorimetry (DSC), Thermogravimetric Analysis (TGA), resistivity, contact angle and mechanical properties was measured, and in vitro biological assays with human mesenchymal stem cells (hMSCs) was evaluated. It was observed that the average diameter of the fibers depends on the AC frequency applied during electrospinning. The FT-IR analysis showed that there was interaction between the PCL and the CNTs, and biological analysis indicated that the blankets of PCL/CNT and PCL/GO are promising for use as a biomaterial / Doutorado / Materiais e Processos de Fabricação / Doutora em Engenharia Mecânica

Orientadores: Ana Flávia Nogueira, Valtencir Zucolotto / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T02:59:18Z (GMT). No. of bitstreams: 1 Almeida_LuizCarlosPimentel_D.pdf: 6880507 bytes, checksum: f7a2c24853f25411226ae9b66a2de97b (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foram estudados filmes finos multicamadas baseados em polímeros condutores, nanotubos de carbono e um derivado de fulereno. Esses filmes foram depositados pela técnica de deposição camada por camada (LbL) via interações eletrostáticas. Esse trabalho está dividido em duas partes: 1-) Filmes LbL baseados no polímero conjugado poli(p-fenilenovinileno) (PPV) e nanotubos de carbono de parede única funcionalizados com grupos carboxílicos (SWNTCOOH) foram preparados em arquitetura de bloco, caracterizados e aplicados como fotoeletrodos em células solares fotoeletroquímicas. A morfologia desses filmes foi avaliada por microscopia de força atômica (AFM) e de epifluorescência, as quais indicaram uma variação morfológica significativa dos filmes após adição de camadas de nanotubos de carbono. A transferência de carga fotoinduzida do polímero condutor PPV para o SWNT-COOH foi analisada por supressão de fotoluminescência (PL). A caracterização fotoeletroquímica foi realizada sob irradiação de luz branca e os fotoeletrodos contendo SWNT-COOH apresentaram valores de fotocorrente de até 7,5 mA cm. A fotocorrente aumentou e tornou-se mais estável quando uma camada do polímero poli(3,4-etilenodioxitiofeno) dopado com poli(4-sulfonato de estireno) (PEDOT:PSS) foi depositada entre o eletrodo ITO e o filme LbL. 2-) Foram preparados filmes LbL baseados no polímero conjugado poli[2-(3-tienil)-etoxi-4-butilsulfonato] de sódio (PTEBS) e no derivado de fulereno C60-F. A caracterizacao fotofísica mostrou a ocorrência de transferência fotoinduzida de carga do PTEBS para o C60-F, a qual foi também demonstrada por meio da geração de fotocorrente obtida quando os filmes (PTEBS/C60-F) foram aplicados como fotoeletrodos em células solares fotoeletroquímicas. Os resultados obtidos fazem dos filmes LbL baseados em semicondutores orgânicos candidatos promissores para conversão de energia solar. / Abstract: In this work, multilayer thin films based on conducting polymers, carbon nanotubes and fullerene derivatives were studied. These films were fabricated by layer-by-layer deposition technique (LbL) through electrostatic interactions. This work is divided in two parts: 1-) LbL films composed of a conducting polymer poly(p-phenylenevinylene) (PPV) and carboxylic acid functionalized singlewalled carbon nanotubes (SWNT-COOH) were prepared in a block architecture, characterized and applied as electrodes in photoelectrochemical solar cells. Film morphology was evaluated by atomic force and epifluorescence microscopies, showing remarkable changes after incorporation of SWNT-COOH layers. The photoinduced charge transfer from the conducting polymer to SWNT-COOH was analyzed by photoluminescence (PL) quenching. Photoelectrochemical characterization was performed under white light and the films containing SWNTCOOH displayed photocurrent values up to 7.5 mA cm. Photocurrent generation was enhanced and became more stable when an intermediate layer of poly(3,4- ethylenedioxythiophene)¿poly(4-styrenesulfonic acid) (PEDOT:PSS) was interposed between the ITO electrode and LbL films. 2-) LbL films based on the conducting polymer sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate] (PTEBS) and fullerene derivative C60-F were fabricated. Photophysical characterization shows the occurrence of photoinduced charge transfer from PTEBS to C60-F, which was also demonstrated by photocurrent generation obtained when (PTEBS/C60-F) multilayer films were applied as electrodes of photoelectrochemical solar cells. All these results make the LbL films based on organic semiconductors promising canditates towards solar energy conversion. / Doutorado / Físico-Química / Doutor em Ciências

An ideal biosensor is a compact and in-expensive device that is able to readily and rapidly detects different types of analytes with high sensitivity and specificity. The affectability of a biosensing methodology is subject to the limit of nanomaterials to transduce the target binding process to an improved perceptible signal, while the selectivity is accomplished by considering the binding and specificity of certain moieties to their targets. Keeping these requirements in mind we have chosen nanomaterials such as carbon nanotubes (CNTs) and gold nanoparticles (AuNPs) that has catalytic properties combined with their size, shape and configuration dependent chemical and physical properties as essential precursors and signaling components for creation of biosensors with tremendous sensitivity. The primary goal of the research work described in this dissertation is to develop and evaluate novel methods to detect various analytes using nanomaterials, at the same time making an affordable architecture for point-of-care (POC) applications. We report here in chapter 3 a simple and new strategy for preparing disposable, paper-based, porous AuNP/M-SWCNT hybrid thin gold films with high conductivity, rapid electron transfer rates, and excellent electrocatalytic properties to achieve multiple analyte electrochemical detection with a resolution that greatly exceeds that of purchased flat gold slides. We further explored the use of nanomaterial-based paper films in more complex matrices to detect analytes such as NADH, which can act as a biomarker for certain cellular redox imbalances and disease conditions. Carbon nanotubes with their large activated surfaces and edge-plane sites (defects) that are ideal for performing NADH oxidation at low potentials without any help of redox mediators minimizing surface fouling in complex matrices is described in chapter 4. With an instrument-free approach in mind we further focused on a colorimetric platform using split cocaine aptamers and gold nanoparticles (AuNPs) to detect cocaine for on-site applications as described in chapter 5. In chapter 5, the split aptamer sequences were evaluated mainly on three basic criteria, the hybridization efficiency, specificity towards the analyte (cocaine), and the reaction time to observe a distinguishable color change from red to blue. The assay is an enzyme-assisted target recycling (EATR) strategy following the principle that nuclease enzyme recognizes probe–target complexes, cleaving only the probe strand releasing the target for recycling. We have also studied the effect of the number of binding domains with variable chain lengths on either side of the apurinic (AP) site. On the basis of our results, we finally shortlisted the sequence combination with maximum signal enhancement fold which is instrumental in development of colorimetric platform with faster, and specific reaction to observe a distinctive color change in the presence of cocaine.

Abstract Carbon nanotubes are a promising material for various applications due to their unique collection of properties. However, carbon nanotube material as such is inert and insoluble, which hampers the true realization of its potential. In order to enhance the applicability of carbon nanotubes, their surface must be modified. This work concerned the chemical modification of single-walled carbon nanotubes (SWNT) by the Birch reduction, which is based on the reduction of the SWNT surface with the valence electron of alkali metal solvated in liquid ammonia. The reduction generates a SWNT anion, which reacts with electrophiles resulting in the covalent attachment of functional groups to the tube surface. In this work, aryl halides or alcohols were used as electrophiles to yield arylated or hydrogenated SWNTs, respectively. At first, the goal was to modify SWNTs as a filler material for polystyrene. The use of five halogenated ethenylphenyl derivatives as electrophiles revealed that the structure of electrophile affected the success of functionalization and the solubility of SWNTs in polystyrene-toluene solution. The most successful functionalization and solubilization of SWNTs were achieved with 1-chloro-4-ethenylbenzene. In the second part, liquid ammonia was replaced with a new solvent, 1-methoxy-2-(2-methoxyethoxy)ethane (diglyme) in order to avoid the restrictions, hazards and inconvenience of its handling. The work concentrated on the study of alkali metal reduction of SWNTs in diglyme by the use of arylation with 4-iodobenzoic acid or 4-chlorobenzoic acid and hydrogenation as model reactions. Li, Na or K was used as an alkali metal while naphthalene or 1-tert-butyl-4-(4-tert-butylphenyl)benzene was used in order to enhance the solvation of electrons. As a result, functionalization was simplified and enhanced. Electrophile affected the functionalization in such a way that arylation was significantly more successful than hydrogenation. The effect of alkali metal and electron carrier varied with electrophile. The most successful hydrogenation was achieved with the complex of Li and 1-tert-butyl-4-(4-tert-butylphenyl)benzene while arylation was the most successful with the complex of K and naphthalene. The solubility of SWNTs in water, ethanol, methanol and dimethylformamide was clearly improved by arylation whereas hydrogenation led to moderate improvement. / Tiivistelmä Hiilinanoputket ovat ainutlaatuisten ominaisuuksiensa vuoksi lupaava materiaali moniin sovelluksiin, mutta liukenemattomuus ja epäreaktiivisuus haittaavat niiden tehokasta hyödyntämistä. Käytettävyyttä voidaan parantaa kemiallisella modifioinnilla. Tässä työssä yksiseinäisiä hiilinanoputkia modifioitiin Birch-pelkistyksellä, joka perustuu putken pinnan pelkistykseen nestemäiseen ammoniakkiin solvatoituneella alkalimetallin valenssielektronilla. Pelkistyksessä hiilinanoputkesta muodostuu anioni, joka reagoi elektrofiilin kanssa johtaen funktionaalisten ryhmien kovalenttiseen sitoutumiseen putken pintaan. Tässä työssä hiilinanoputkia aryloitiin käyttämällä aryylihalideja elektrofiilinä tai vedytettiin käyttämällä alkoholia. Aluksi tavoitteena oli hiilinanoputkien modifiointi sellaiseen muotoon, että niitä voitaisiin käyttää polystyreenin täyteaineena. Viittä aryylihalidia käyttämällä havaittiin, että elektrofiilin rakenne vaikutti funktionalisoinnin määrään ja putkien liukoisuuteen polystyreeni-tolueeni-liuokseen. 1-Kloori-4-etenyylibentseenillä saavutettiin onnistunein arylointi ja paras liukoisuus. Työn toisessa osassa luovuttiin ammoniakin käytöstä siihen liittyvien rajoitteiden ja haittojen vuoksi. Keskityttiin hiilinanoputkien alkalimetallipelkistyksen tutkimiseen uudessa liuottimessa, 1-metoksi-2-(2-metoksietoksi)etaanissa (diglyymi). Mallireaktioina käytettiin arylointia 4-jodibentsoehapolla tai 4-klooribentsoehapolla ja vedytystä alkoholilla. Ammoniakin korvaaminen diglyymillä yksinkertaisti ja tehosti funktionalisointia. Reaktiot suoritettiin eri alkalimetalleilla (Li, Na tai K). Naftaleenia tai 1-tert-butyyli-4-(4-tert-butyylifenyyli)bentseeniä käytettiin elektronien solvatoinnin parantamiseksi. Elektrofiilin rakenne vaikutti funktionalisointiin siten, että aryylihalidi johti huomattavasti onnistuneempaan funktionalisointiin kuin alkoholi. Alkalimetallin ja elektroninkantajamolekyylin vaikutus vaihteli elektrofiilin mukaan. Litiumin käyttö 1-tert-butyyli-4-(4-tert-butyylifenyyli)bentseenin kanssa johti onnistuneimpaan vedytykseen. Kaliumin käyttö naftaleenin kanssa johti onnistuneimpaan arylointiin. Hiilinanoputkien liukoisuus vaihteli elektrofiilin mukaan. Arylointi paransi selkeästi hiilinanoputkien liukoisuutta veteen, etanoliin, metanoliin ja dimetyyliformamidiin. Vedytyksen vaikutus liukoisuuteen oli vähäisempi.

Le développement de circuits mesoscopiques avec une architecture hybride cette dernière décennie a permis d’étudier l’interaction lumière matière dans son aspect fondamental avec des photons dans le régime micro-ondes. Ces développements permettent aujourd’hui d’étudier cette interaction dans le domaine terahertz, gamme spectrale s’étendant de 0.1 THz à 10 THz (0.4 meV-41,3 meV). L’apparition de sources performantes et de méthodes de spectroscopie efficaces telles que la spectroscopie dans le domaine temporel sont des outils utilisables pour l’étude de l’interaction lumière matière dans ce domaine spectral. Dans ce travail de thèse, nous avons développé un outil afin d’étudier cette interaction dans son aspect le plus fondamental composé d’un nanotube de carbone en régime de boîte quantique et d’une cavité térahertz. Le nanotube de carbone est un élément d’autant plus adapté que sa structure électronique est régie par des énergies dont la fréquence équivalente se situe dans le terahertz. La cavité térahertz est un "split ring resonator". Le travail s’est décomposé en deux aspects, avec dans un premier temps le développement d’un banc de spectroscopie térahertz large bande (0.3 THz-20 THz) dans le domaine temporel pour l’étude des résonateurs. En utilisant un procédé original de contrôle du front d’onde d’émission de l’antenne, nous démontrons que le champ térahertz est focalisé en limite de diffraction ce qui ouvre la possibilité d’étudier des résonateurs uniques. Dans un second temps, des mesures de transport électronique ont été effectuées afin de mettre en évidence un couplage entre le résonateur et la boîte quantique. Un couplage avec un mode bosonique est observé. La conductance de ces états est modulée par la source de photons utilisée dans cette étude. Cependant, l’énergie du mode est inférieure à celle observée par les mesures de spectroscopie ne permettant pas de conclure de manière définitive sur l’origine de ce mode. / In the last ten years, research has been devoted to the development of hybrid architecture mesoscopic circuit to study the ligh-matter interaction in the microwaves range. These improvements allow us to study this interaction in the terahertz range extending from 0.1 THz to 10 THz (0.4 meV - 41.3 meV). Moreover, new efficient sources and new spectroscopy schemes like time domain spectroscopy set-up are some tools that can be used to study the light-matter interaction in this range. In this work, we developed a paradigm to study the interaction in the fundamental aspect composed of a carbon nanotube in a quantum dot regime embedded in a terahertz cavity. Carbon nanotube quantum dot is well adapted because of its electronic levels which are separated by energy in the terahertz range. The cavity used for the study is a "split ring resonator". This thesis is decomposed in two parts. Firstly, we built an ultrabroadband terahertz time domain spectroscopy set-up (0.3 THz -20 THz) to study the terahertz resonators. We demonstrated that the terahertz field is focused at the diffraction limit by exciting the antenna with an original scheme based on a control wavefront. Then, electronic transport measurements have been done to highlight the coupling between the cavity and the quantum dot. A coupling with a bosonic mode is observed. The conductance of these states is modified by the source that we used in this work. However, the energy of the observed mode is lower than the fundamental energy mode of the cavity that do not allow us to conclude about the origin of this mode.

Carbon nanotubes (CNTs) and gold nanoparticles (AuNPs) are widely used for sensing applications due to their distinctive electrical and optical properties, and we have explored the development of methods that enable the incorporation of these nanomaterials into new and improved sensing devices. As a means for fabricating simple, low-cost and fast detection platforms for various applications, we have developed paper-based electrochemical detection platforms based on CNTs or platinum nanoparticle (PtNP)-CNT composite materials. We describe the use of a paper-based, low density, a three-dimensional thin film of interconnected CNTs as an electrode material. We studied the electrochemical properties of these paper-based CNT electrodes and demonstrated their use as an electrochemical sensor for the sensitive detection of guanine-based nucleotides. We further describe the functionalization of this paper-based electrode by fabricating a PtNP-SWCNT hybrid film via a vacuum filtration-based method. The interconnected PtNP structure formed on top of the CNT-coated paper was directly used as an electrocatalyst for methanol oxidation. Compared to paper-based PtNP-SWCNT hybrid films formed by electrochemical deposition, hybrid films formed by vacuum filtration showed a higher electrochemical surface area and enhanced electrocatalytic response to methanol oxidation. We have also developed methods based around DNA-modified AuNPs, which offer an excellent colorimetric platform for target detection. The DNA density on the surface of modified AuNPs affects enzymatic activity, colloidal stability of AuNPs, the orientation of the probe DNA and its hybridization efficiency. The combination of all these factors ultimately dictates the reaction time and sensitivity of colorimetric assays. We demonstrate the use of DTT as a modulator to control DNA surface coverage on the surface of AuNPs. Using this DTT treatment and a novel probe for exonuclease III activity, we have developed a colorimetric assay based on DTT-treated, DNA-modified AuNPs that can achieve more sensitive and rapid detection of DNA and enzymes relative to existing sensor platforms.

This thesis is divided into two parts; the first part presents results on the effect of the flow of fluids and electrochemical bias on single walled carbon nanotubes (SWNT). Issues pertaining to the entry of water into the cylindrical pores of the SWNT and its freezing dynamics have also been addressed in the first part of the thesis. The second part of the thesis deals with Raman scattering studies of iron perovskite namely CaFeO3 and La0.33Sr0.67FeO3 across their charge-disproportionation transition temperatures. PART 1 Chapter 1: Introduction This chapter presents an overview of the systems studied in this thesis, i.e., (i) SWNT and (ii) iron perovskite’s containing iron in Fe4+(d4) state, namely CaFeO3 and La0.33Sr0.67FeO3. It also contains an introduction to the two spectroscopic techniques used in the present thesis, namely Raman scattering and Nuclear Magnetic Resonance. A quantum mechanical picture of Raman scattering, in general, and resonance Raman scattering in particular along with a brief introduction to the apparatus used both for the micro Raman and the low temperature experiments is presented in this chapter. A general introduction to Nuclear Magnetic Resonance (NMR) is also given with an emphasis on various interactions leading to the broadening of the NMR absorption linewidths. Chapter 2: Carbon nanotube liquid flow sensors This chapter presents experimental results and theoretical understandings of the generation of electrical signals by flowing polar/ionic liquids over a mat of SWNT. We first present experimental findings that the flow of a variety of liquids on SWNT bundles induces an electrical signal (voltage/current) in the sample along the direction of the flow. The electrical response is found to be a logarithmic function of the flow speed over a wide range. The magnitude of the signal generated depends sensitively on the ionic conductivity and the polar nature of the liquid and weakly on the viscosity of the liquid. Furthermore its direction can be controlled by electrochemical biasing of the nanotubes. The ratio of the open circuit voltage to the short circuit current is found to be governed by the nanotube resistance. These experimental findings are inconsistent with the conventional idea of a streaming potential as the possible cause. Our measurements suggest that the dominant mechanism responsible for this highly sub-linear response should involve a direct forcing of the free charge carriers in the nanotubes by the fluctuating Coulombic field of the liquid flowing past it. Two alternative understandings of the experimental findings are also presented in this chapter. The first mechanism invokes the idea of a “pulsating ratchet” whereby the charge carriers in the nanotubes experience an asymmetric spatial bias because of the shear-induced deformation of the ion-plus-polar atmosphere at the liquid-solid interface temporally modulated by the liquid flow. In addition, we also propose that experimental findings can be understood qualitatively in terms of three interrelated ideas: (a) Induced friction: The fluctuating charge density of the ions close to the nanotube couples coulombically to the charge carriers in the nanotube and, therefore, offers a friction to the motion of these charge carriers (in addition to the Ohmic friction intrinsic to the carbon nanotubes); (b) Flow-induced drag: In virtue of the above frictional coupling, an imposed liquid flow drags the charge carriers along through the nanotube; (c) Reduction of induced friction at high flow speeds: The space-time correlated Coulombic fluctuations, inherent to the liquid electrolyte, are advected by the liquid flow, and thus get Galilean boosted (Doppler shifted) as seen in the mean rest frame of the drifting carriers in the nanotube. This would cause a reduction of the frictional grip to the motion of the charge carriers in the nanotube with increasing flow speed resulting in a sublinear dependence of the charge drift-velocity (electrical response) on the liquid flow speed. With the above in mind, a quantitative derivation of these frictional effects, first from a heuristic argument, and then analytically from a Langevin-equation treatment have been presented. Chapter 3: Direct generation of voltage and current by gas flow over carbon nanotubes and semiconductors Having obtained experimental evidence of the generation of liquid flow induced electrical signals over single-walled carbon nanotubes, it was only natural to look for the same effect by flowing gases over nanotubes. We show here a direct generation of measurable voltages and currents when gas flows at modest speeds of a few meters per second over single-walled carbon nanotubes . Interestingly, unlike the previous effect (generation of voltages by flow of liquids over single-walled carbon nanotubes), this effect is not specific to single-walled carbon nanotubes and occurs for a wide variety of solids, including single and multi-walled carbon nanotubes, doped semiconductors and metals. Moreover, the gas flow induced signals depend quadratically on the gas flow velocities. This is in sharp contrast to the results obtained by flowing liquids over single-walled carbon nanotubes where the liquid flow generated signal was found to be logarithmically dependent on the flow velocities. In this chapter we provide evidence that the underlying mechanism for the gas flow generated electrical signal is an interplay of Bernoulli’s principle and the Seebeck effect: Pressure difference along streamlines gives rise to temperature difference across the sample which, in turn, produces the measured voltage. Chapter 4: Water at nanoscale confined in single-walled carbon nanotubes studied by NMR In this chapter, we seek experimental evidence of the occupancy of water in the cylindrical pores of the nanotubes. Proton NMR studies have been carried out as a function of temperature from 210 K to 300 K of water confined within SWNT. The NMR lineshape at and below the freezing point of bulk water is asymmetric which can be decomposed into a sum of two Lorentzians. The intensities of both the components decrease with lowering of temperature below 273 K, one component L1 vanishing below 242 K and the other component L2 below 217 K. Following the simulations of Koga et al. (Nature, 412, 802, 2001) showing that the radial density profile of confined water in SWNT has a distribution peak at the center which disappears below the freezing temperature, the L1 component is associated with the protons of the water molecules at the center and the L2 component is associated with protons of water molecules associated at a distance ~ 3Å away from the walls of the nanotubes. In this scenario the complete freezing of the water at ~ 212 K is preceded by the withdrawal of the water molecules from the center of the nanotubes. Chapter 5: Electrochemical tuning of band structure of single walled carbon nanotubes probed by in-situ resonance Raman scattering The work presented in this chapter is motivated by the experimental observation that SWNT have excellent actuating properties, i.e, porous sheets of carbon nanotubes were shown to suffer length changes when subjected to electrochemical bias, with action observed up to 1 KHz. The fast response of the nanotube actuator rules out any mechanism related to the intercalation of ions as is applicable to the case of the polymer actuators. This chapter presents results of in-situ resonance Raman scattering of SWNT investigated under electrochemical biasing. The experimental results show that the intensity of the radial breathing mode varies significantly in a non-monotonic manner as a function of the cathodic bias voltage, but does not change appreciably under anodic bias. The tangential mode is, however, not affected. These results can be quantitatively understood in terms of the changes in the energy gaps between the one-dimensional van Hove singularities in the electron density of states arising possibly due to the alterations in the overlap integral of π-bonds between the p-orbitals of adjacent carbon atoms. This chapter also contains results from ab-initio restricted Hartree Fock calculations in a simplistic geometry where a nanotube is surrounded by two concentric rings of ions. The ab-initio calculation results suggest that the dominant contribution to the strain developed in the nanotubes originates from the electrostatic interactions between the ions and the delocalized π electrons as compared to the doping effects. PART 2 Chapter 6: Raman scattering in CaFeO3 and La0.33Sr0.67FeO3 across the charge disproportionation phase transition Temperature dependent micro-Raman studies of orthorhombic CaFeO3 and rhombohedral La0.33Sr0.67FeO3 were carried out with an aim to study the role of phonons in the formation of the charge disproportioned state (Fe4+ → Fe5++Fe3+) below the transition temperature (Tco) of 290 K and 200 K, respectively. Shell model lattice dynamics calculations were performed for CaFeO3 to assign the Raman modes and determine their vibrational pattern. Temperature dependence of the peak positions and peak widths of various modes for both the systems show distinct changes across their respective transition temperatures. In CaFeO3 the symmetric stretching mode at 707 cm−1 splits into two modes, 707 cm−1 and 684 cm−1 . Interestingly, the 707 (684) cm−1 mode appears only in HH(HV) polarization. In comparison, the Raman band at 704 cm−1 in La0.33Sr0.67FeO3 which has been assigned to the Raman forbidden symmetric stretching mode, disappears below Tco. In addition, two modes at 307 cm−1 and 380 cm−1 of La0.33Sr0.67FeO3 approach each other at Tco. Our experiments show that for both the systems, CaFeO3 and La0.33Sr0.67FeO3, the lattice distortion changes across Tco. Chapter 7: Summary and future outlook The last chapter summarizes our main findings reported in the thesis. It also contains possible future studies which are worth pursuing to add further insights in the issues addressed.

Cette thèse est consacrée à l'étude expérimentale par spectroscopie de photoluminescence de nanotubes de carbone nus et fonctionnalisés. Les nanotubes étant formés exclusivement d'atomes de surface, leurs propriétés optiques peuvent être grandement altérées, mais aussi contrôlées, par interaction avec l'environnement physico-chimique. Un dispositif de microscopie confocale à l'échelle de l'objet unique et à température cryogénique est développé pour l'étude de la luminescence de nanotubes déposés sur substrat. La variété des profils spectraux observés est interprétée en terme d'un couplage entre excitons localisés et phonons acoustiques unidimensionnels dont le spectre peut être altéré aux basses énergies. Ce mécanisme explique notamment l'observation originale de raies très fines, de largeur inférieure à 500 µeV. La fonctionnalisation non-covalente des nanotubes par des molécules de colorants (porphyrines) introduit une nouvelle voie d'excitation optique par un transfert d'énergie très efficace. Le suivi physico-chimique de la réaction d'adsorption nous informe sur la couverture et l'affinité des molécules sur les nanotubes. Une étude de photoluminescence sur composés uniques résolue en polarisation montre une forte anisotropie du transfert d'énergie gouvernée par des effets d'antenne à proximité du nanotube. Enfin, le colorant peut être utilisé comme cellule d'absorption de référence pour évaluer la section efficace d'absorption des nanotubes. Une nette évolution avec l'angle chiral de l'espèce est notamment observée pour l'absorption à la résonance optique S22. / This manuscript presents an experimental study on pristine and functionalized single-wall carbon nanotubes by means of photoluminescence spectroscopy. Due to nanotubes original one-layer structure, the physico-chemical environment can greatly alter their optical properties, introducing in the same time a way to control these properties. Luminescence signals from single substrate desposited nanotubes are studied with a home-made confocal microscope at cryogenic temperatures. The large variety of observed spectral profiles is interpreted in term of an unified coupling between localized excitons and unidimensionnal acoustic phonons. In particular, a local gap in the low energy phonon spectrum leads to narrow lines with width lower than 500 µeV. Nanotubes non-covalently functionalized with dye molecules (porphyrins) show an original absorption feature at 2.8 eV involving a very efficient energy transfer. Molecules coverage and affinity on the nanotube wall are evaluated from the adsorption thermodynamic equilibrium. A polarized photoluminescence study at the single compound scale reveals that the energy transfer shows strong anisotropy owing to antenna effects in the vicinity of the nanotube. Finally, the dye molecule can be used as an absorptive unit cell to calculate the absorption cross section of carbon nanotubes. A clear evolution is found at the S22 optical resonance with respect to the chiral angle of the species.

abstract: Electrostatic Discharge (ESD) is a unique issue in the electronics industry that can cause failures of electrical components and complete electronic systems. There is an entire industry that is focused on developing ESD compliant tooling using traditional manufacturing methods. This research work evaluates the feasibility to fabricate a PEEK-Carbon Nanotube composite filament for Fused Filament Fabrication (FFF) Additive Manufacturing that is ESD compliant. In addition, it demonstrates that the FFF process can be used to print tools with the required accuracy, ESD compliance and mechanical properties necessary for the electronics industry at a low rate production level. Current Additive Manufacturing technology can print high temperature polymers, such as PEEK, with the required mechanical properties but they are not ESD compliant and require post processing to create a product that is. There has been some research conducted using mixed multi-wall and single wall carbon nanotubes in a PEEK polymers, which improves mechanical properties while reducing bulk resistance to the levels required to be ESD compliant. This previous research has been used to develop a PEEK-CNT polymer matrix for the Fused Filament Fabrication additive manufacturing process / Dissertation/Thesis / Masters Thesis Engineering 2020

Junctions are the key component for 3D carbon nanotube (CNT)-graphene seamless hybrid nanostructures. Growth mechanism of junctions of vertical CNTs growing from graphene in the presence of iron catalysts was simulated via quantum mechanical molecular dynamics (QM/MD) methods. CNTs growth from graphene with iron catalysts is based on a ‘‘base-growth’’ mechanism, and the junctions were the mixture of C-C and Fe-C covalent bonds. Pure C-C bonded junctions could be obtained by moving the catalyst during CNT growth or etching and annealing after growth. The growth process of 3D CNT-graphene junctions on copper templates with nanoholes was simulated with molecular dynamic (MD) simulation. There are two mechanisms of junction formation: (i) CNT growth over the holes that are smaller than 3 nm, and (ii) CNT growth inside the holes that are larger than 3 nm. The growth process of multi-layer filleted CNT-graphene junctions on the Al2O3 template was also simulated with MD simulation. A simple analytical model is developed to explain that the fillet takes the particular angle (135°). MD calculations show that 135° filleted junction has the largest fracture strength and thermal conductivity at room temperature compared to junctions with 90°,120°, 150°, and 180° fillets. The tensile strengths of the as-grown C–C junctions, as well as the junctions embedded with metal nanoparticles (catalysts), were determined by a QM/MD method. Metal catalysts remaining in the junctions significantly reduce the fracture strength and fracture energy. Moreover, the thermal conductivities of the junctions were also calculated by MD method. Metal catalysts remaining in the junctions considerably lower the thermal conductivity of the 3D junctions.