Metallic nanostructures supporting surface plasmon modes can concentrate optical fields, and enhance luminescence processes from the metal surface at plasmonic hotspots. Such nanoplasmonic metal luminescence contributes to the spectral background in surface-enhanced Raman spectroscopy (SERS) measurements and is helpful in bioimaging, nano-thermometry, and chemical reaction monitoring applications. Despite increasing interest in nanoplasmonic metal luminescence, little attention has been paid to investigating its dependence on voltage modulation. Also, the hyphenated electrochemical surface-enhanced Raman spectroscopy (EC-SERS) technique typically ignores voltage-dependent spectral background information associated with nanoplasmonic metal luminescence due to limited mechanistic understanding and poor measurement reproducibility. In this thesis, we combine the experimental observations and theoretical study on dynamic Faradaic & non-Faradaic modulated nanoplasmonic metallic luminescence and molecular vibrational Raman from hotspots at the electrode-electrolyte interfaces using multiple novel nano-optoelectrodes. Our work represents a critical step toward the general application of nanoplasmonic metal luminescence signals in optical voltage biosensing, hybrid optical-electrical signal transduction, and interfacial electrochemical monitoring. / Master of Science / Understanding the non-Faradaic and Faradaic process pathway is crucial for unraveling reaction mechanisms, developing efficient catalysts, designing bionsensing methodology, energy conversion and cellular stimulator (1-7). Advances in spectroscopic techniques( 8, 9) and computational models (3, 10) have facilitated the investigation of the non-Faradic and Faradaic processes. Unlike bulk reactions, interfacial electrochemical reactions occur in nanometer-thin layers (3, 11), necessitating highly sensitive detection methods. A significant challenge is background interference from bulk electrolytes and electrodes, often obscuring weak signals from the interfacial region – traditional spectroelectrochemistry struggles to match the high temporal resolution requirement due to noise (12, 13). Surface plasmons have become a promising solution for enhancing the sensitivity of spectroelectrochemical techniques (14, 15). Surface plasmons are collective oscillations of electrons at the metal-dielectric interface, which can focus and intensify optical fields at the nanoscale (16), boosting diverse nonlinear emission signals, including fluorescence, Raman scattering, and harmonic generation (17-23). By utilizing surface plasmons, spectroelectrochemistry techniques have shown promise in detecting interfacial activities with high sensitivity. In this thesis, we introduce a pioneering dual-channel in situ EC-SERS methodology, which harnesses the synergy between plasmon-enhanced vibrational Raman scattering (PE-VRS) and plasmon-enhanced electronic Raman scattering (PE-ERS) interfacial signals to monitor and analyze the Faradaic and non-Faradaic process at the electrode-electrolyte interfaces.

This dissertation is to obtain an overall understanding of the crack path selection in adhesively bonded joints. Using Dow Chemical epoxy resin DER 331® with various levels of rubber concentration as an adhesive, and aluminum 6061-T6 alloy with different surface pretreatments as the adherends, both symmetric and asymmetric double cantilever beam (DCB) specimens are prepared and tested under mixed mode fracture conditions in this study. Post-failure analyses conducted on the failure surfaces indicate that the failure tends to be more interfacial as the mode II component in the fracture increases whereas more advanced surface preparation techniques can prevent failure at the interface. Through mechanically stretching the DCB specimens uniaxially until the adherends are plastically deformed, various levels of T-stress are achieved in the specimens. Test results of the specimens with various T-stresses demonstrate that the directional stability of cracks in adhesive bonds depends on the T-stress level. Cracks tend to be directionally stable when the T-stress is compressive whereas directionally unstable when the T-stress is tensile. However, the direction of crack propagation is mostly stabilized when more than 3% mode II fracture component is present in the loading regardless of the T-stress levels in the specimens. Since the fracture sequences in adhesive bonds are closely related to the energy balance in the system, an energy balance model is developed to predict the directional stability of cracks and the results are consistent with the experimental observations. Using the finite element method, the T-stress is shown to be closely related to the specimen geometry, indicating a specimen geometry dependence of the directional stability of cracks. This prediction is verified through testing DCB specimens with various adherend and adhesives thicknesses. By testing the specimens under both quasi-static and low-speed impact conditions, and using a high-speed camera to monitor the fracture sequence, the influences of the debond rate on the locus of failure and the directional stability of cracks are investigated. Post-failure analyses suggest that the failure tends to be more interfacial when the debond rate is low and tends to be more cohesive when the debond rate is high. However, this rate dependence of the locus of failure is greatly reduced when more advanced surface preparation techniques are used in preparing the specimens. The post-failure analyses also reveal that cracks tend to be more directionally unstable as the debond rate increases. Finally, employing interface mechanics and extending the criteria for the direction of crack propagation to adhesively bonded joints, the crack trajectories for directionally unstable cracks are predicted and the results are consistent with the overall features of the crack paths observed experimentally. / Ph. D.

The problem of a thin elastomeric layer confined between two stiff adherends arises in numerous applications such as microelectronics, bio-inspired adhesion and the manufacture of soft biomedical products. A common requirement is that the debonding of the elastomeric layer from the adherends be controlled to avoid undesirable failure modes. This level of control may necessitate understanding the collective role of the interfacial adhesion, material properties, part geometries, and loading conditions on the debonding. Analytical and numerical approaches using the finite element method and a cohesive zone model (CZM) for the interfacial debonding are used in this dissertation to delineate the role of the afore-mentioned parameters on the initiation and propagation of debonding for both rigid and non-rigid adherends. Extensively studied in the dissertation is the debonding of a semi-infinite relatively stiffer adherend from an elastomer layer with its other surface firmly bonded to a rigid base. The adherend is pulled upwards by applying normal displacements either on its entire unbonded surface or on the edge of its part overhanging from the elastomer layer. The adherend and the elastomeric layer materials are assumed to be linear elastic, homogeneous and isotropic and the elastomer is assumed to be incompressible. Viscoelasticity of the elastomer is considered in the first part of the work. Plane strain deformations of the system with a bilinear traction-separation (TS) relation in the CZM are analyzed. Two non-dimensional numbers, one related to the layer confinement and the other to the interfacial TS parameters, are found to determine if debonding initiates at interior points in addition to at corner points on the adherend/elastomer interface, and if adhesion-induced instability is exhibited. This work is extended to axisymmetric problems in which debonding can take place at both interfaces. Motivated by an industrial demolding problem, numerical experiments are conducted to derive insights into preferential debonding at one of the two interfaces, including for curved adherends. Results reported herein should help engineers design an elastomer layer sandwiched between two adherends for achieving desired failure characteristics. / Ph. D.

Concrete is the most widely used construction material in the world. Given its relative availability, strength, economy, and versatility to fit various applications, the material has been incorporated in roadways, bridges, buildings, and a host of other infrastructure projects. Oftentimes, concrete will be exposed to several environmental conditions that ultimately affect its durability and lifespan. These conditions include repeated freezing and thawing, chloride intrusion, sulfate attack, alkali-silica reaction, and many others. Given the age and condition of American infrastructure, concrete structures throughout the country need repair or rehabilitation. Often this repair includes the removal of degraded or damaged concrete and the application of an overlay material. There are several factors affecting the bond performance of the newly formed substrate-repair concrete, such as surface roughness, overlay material, and substrate moisture condition. The work presented in this thesis is dedicated to understanding the effect of substrate moisture condition on the overlay transition zone (OTZ) of the substrate-repair concrete. The substrate moisture condition can significantly impact the microstructure characterization of the OTZ. If the substrate is too dry, then it may absorb water from the repair material, reducing the local water-to-cement (w/c) ratio in the OTZ. Conversely, if the substrate is too wet, then the w/c ratio of the OTZ will be locally increased. In both scenarios, the interfacial bond strength is expected to be modified due to the change in the local w/c ratio. To understand this effect, various test methods and degradation mechanisms were explored. Initially, substrate-repair concrete specimens were prepared utilizing three separate substrate moisture conditions: saturated surfaced dry (SSD), sub-saturated surface dry (Sub-SSD), and oven dry (OD). After allowing these samples to cure, the strength and ion penetration risk were evaluated. The bond strength of the samples was evaluated through flexural strength testing and fracture energy determined through the RILEM draft tests. The OTZ ion penetration risk was evaluated by conducting rapid chloride penetration test (RCPT) on samples prepared with the three substrate moisture conditions. Furthermore, to determine the effect of repeated freezing and thawing on the OTZ and flexural strength, additional samples were created with the three moisture conditions. After allowing these samples to cure, they were subjected to ASTM C666 and were tested to observe their flexural strength. Another important performance indicator of concrete elements is its resistance to chloride ion penetration and corrosion. Since many structural elements are designed with steel reinforcement, chloride ion penetration represents a critical parameter in projecting material performance, since chloride ions will accelerate the rate of steel corrosion. Oftentimes, a key element in projecting this performance is identifying the rate at which ions diffuse through the material. There remain many established techniques to identify this rate of diffusion and derive a chloride diffusion coefficient; however, many of them are either destructive or qualitative in nature. In recent years, transmission X-ray microscopy (TXM) has been employed to non-destructively track diffusion and develop diffusion coefficients. The work presented in this thesis surrounds the efforts of incorporating TXM experiments at Virginia Tech. This work initially utilized a SkyScan 1174 μCT, and additional work in this thesis presents the design and construction of a dental X-ray system based on the checking ion penetration (CHIP) design. This system can conduct TXM experiments utilizing a dental X-ray as the source. The research, design, and construction of the CHIP system is discussed in this thesis. Ultimately, the research in this thesis has not observed any significant relationship between substrate moisture condition and overlay bond strength. There does appear to be an increase in chloride ion resistance for drier substrates, suggesting that pre-wetting the surface increases penetrability of the interface. / Master of Science / Concrete is the most widely used construction material in the world. Given its relative availability, strength, economy, and versatility to fit various applications, the material has been incorporated in roadways, bridges, buildings, and a host of other infrastructure projects. Oftentimes, concrete will be exposed to several environmental conditions that ultimately affect its durability and lifespan. These conditions include repeated freezing and thawing, chloride intrusion, sulfate attack, alkali-silica reaction, and many others. These environmental conditions ultimately degrade the material by inducing cracks, exposing steel reinforcement, and spalling. When the concrete has experienced significant deterioration, repair and rehabilitation of the damaged section must be performed. Most often, this repair consists of the removal of damaged concrete and the application of an overlay material to prevent further deterioration. The topics discussed in this thesis evaluate the optimum substrate conditions prior to an overlay application and the implementation of techniques to evaluate deterioration mechanisms. There are several substrate conditions that will affect bonding with the overlay material, including surface roughness, moisture conditions, and overlay type. This paper focused on the moisture condition and what effect this had on bond strength and resistance to chloride intrusion. This effect was studied in laboratory conditions and under environmental conditions such as rapid freezing and thawing. Several different deterioration mechanisms may contribute to concrete degradation. The research presented in this thesis also aimed to evaluate chloride ion diffusion. To evaluate this mechanism, two systems were explored with the intent of conducting transmission X-ray microscopy (TXM). With TXM, chloride ion diffusion can be tracked to determine the rate at which ions diffuse through the concrete. The two systems explored were an X-ray computed tomography scanner and a dental X-ray system. Both systems can conduct TXM, and this paper presents the efforts dedicated to developing them for this technique at Virginia Tech. Ultimately, the research in this thesis has not observed any significant relationship between substrate moisture condition and overlay bond strength. There does appear to be an increase in chloride ion resistance for drier substrates, suggesting that pre-wetting the surface increases penetrability of the interface.

Die Ladungsinjektion (-extraktion) an einer Schnittstelle spielt in der organischen Elektronik eine entscheidende Rolle, da sie die Leistung des Bauelements stark beeinflusst. Eine der effizientesten Methoden zur Optimierung der Energiebarrieren für die Injektion ist die Modifikation der Austrittsarbeit der Elektroden. In dieser Dissertation untersuchen wir die Modifikation der Austrittsarbeit von Au(111) durch dithiol-terminiertes Polyethylenglykol (PEG(thiol)) sowie deren Abhängigkeit von der Anzahl der PEG-Wiederholungseinheiten. In beiden Fällen beobachten wir, dass die Austrittsarbeit des Au(111) durch eine Monoschicht PEG(thiol)-Moleküle reduziert wird. Unsere Berechnungen zeigen, dass diese Änderung der Austrittsarbeit hauptsächlich durch (i) die Ladungsumlagerung aufgrund der Chemisorption und (ii) das intrinsische Dipolmoment der PEG(thiol)-Monoschicht verursacht wird. Die Größe des letzteren Beitrags hängt spürbar von der Anzahl der Wiederholungseinheiten ab und bewirkt somit eine Variation in der Reduktion der Austrittsarbeit. Das oszillatorische Verhalten spiegelt einen ausgeprägten Odd-Even-Effekt wider. Dadurch kann die Austrittsarbeit der Metallelektrode unter Berücksichtigung des Odd-Even-Effekts gesteuert werden. Die Konvergenz der selbstkonsistenten Felditeration für unsere Systeme ist nicht garantiert. Um die Konvergenz zu verbessern, schlagen wir die Verwendung eines speziell auf die FP-LAPW-Methode zugeschnittenen Mischalgorithmus vor. In einem auf Ag(111) basierenden System zeigt sich, dass eine Struktur mit drei Leerstellen in der Substratschicht besonders stabil ist. Dabei ist eine kontinuierliche Abnahme der Austrittsarbeit des Ag(111) feststellbar. Ähnlich wie beim Au(111) manifestiert sich der Odd-Even-Effekt, der auf das Dipolmoment der Molekularschicht zurückzuführen ist. / Charge injection (extraction) at an interface plays a crucial role to organic electronics because this injection (extraction) heavily affects the device performance. One of the most efficient way to optimize energy barriers of the injection (extraction) is modifying the work function of electrodes. In this dissertation, we investigate the modification of work function of Au(111) and Ag(111) induced by the dithiol-terminated polyethylene glycol (PEG(thiol)) as well as a dependence of the work function change on different numbers of PEG repeat units. We find that the work function of the Au(111) is reduced by a monolayer of PEG(thiol) molecules. Overall, our calculations indicate that the work function change is mainly induced by (i) the charge rearrangement due to chemisorption and (ii) the intrinsic dipole moment of the PEG(thiol) monolayer. The magnitude of the latter contribution noticeably depends on the number of repeat units and, thus, causes a variation in the reduction of the work function. The oscillatory behavior reflects a pronounced odd-even effect. As a result, the work function of the metal electrode would be controlled by considering the odd-even effect. Unfortunately, the convergence of the self-consistent field iteration is not guaranteed for our investigated systems. To make the smooth convergence, a mixing algorithm, which is applicable to FP-LAPW method, is devised. We add the Kerker preconditioner as well as further improvements to Pulay’s direct inversion in the iterative subspace. Using this method, one can avoid charge sloshing and noise in the exchange-correlation potential. This method is also implemented in the exciting code. We find the decrease of the work function of the Ag(111) surface is always presented. Similar to the Au(111) case, the odd-even effect is revealed, arising from the dipole moment of the molecular layer.

Liquid metal batteries are discussed today as an economic grid-scale energy storage, as required for the deployment of fluctuating renewable energies. These batteries consist of three stably stratified liquid layers: two liquid metal electrodes are separated by a thin molten salt electrolyte, this way forming an electrochemical concentration cell. The completely liquid interior, which is on the one hand very beneficial for the energy efficiency, also poses some major challenges on the other hand. Strong cell currents in combination with electromagnetic fields make liquid metal batteries highly susceptible to various kinds of magnetohydrodynamic instabilities. In particular, the so-called metal pad roll instability, which can drive uncontrollable wave motions in both interfaces, was identified as a key limiting factor for the operational safety. The metal pad roll instability is well known from conceptually similar aluminum reduction cells, but still poorly understood in the framework of liquid metal batteries. Mainly by developing analytical wave models, but also by employing numerical simulations and by setting up a newly designed wave experiment, the present thesis pursues the goal of providing a better understanding of interfacial wave dynamics and the manifestation of the metal pad roll instability in liquid metal batteries. As a main result, a three-layer formulation of standing gravity-capillary waves reveals that the pressure coupling between the two interfaces plays a crucial role in the cell stability. Three different coupling regimes, which partially involve novel types of interfacial wave instabilities, are identified and classified by two dimensionless parameters. Building on this theoretical work, the wave experiment is exploited to further investigate different metal pad roll-related wave properties. The crucial importance of the contact line dynamics is emphasized and viscous damping, which is important for the estimation of instability onsets, is discussed as a function of the layer heights. Finally, a hybrid interfacial sloshing model is formulated and equipped with recently derived two-layer damping rates to account for viscous dissipation. The model allows to study and interpret the forced wave mechanics in the wave experiment as a function of eight dimensionless parameters and can, as an additional application, be exploited to optimize mixing in orbitally shaken bioreactors. As a further key result, the sloshing model reveals the formation of novel spiral wave patterns under the effect of strong damping.

Monolayers of the cationic surfactant hexadecyltrimethylammonium halide (CTAX, where X = F¯, Cl¯, Br¯, and I¯) have been studied at the air-water and oilwater interfaces. At the air-water interface, the effects of the halide counterion and the addition of counterion were investigated. Sum-frequency spectroscopy (SFS), ellipsometry, and surface tensiometry indicated that the counterion changed the efficiency and effectiveness of the surfactant, both decreasing in the order of Br¯> Cl¯>F¯. The addition of salt in the form of 0.1 M KX was found to reduce the cmc but had little effect on the limiting area per molecule attained at the cmc, which increased from 44 Ų for CTAB to 65 Ų for CTAC and ca. 94 Ų for CTAF. Neither SFS nor ellipsometry provided any firm evidence for specific effects of the halide ions on the structure of the surfactant monolayers. For CTAB monolayers in the absence of excess electrolyte, the effect of area per molecule on the sum-frequency (SF) spectra was studied. Mixed monolayers of CTAB and tetradecane at the air-water interface exhibit a first-order phase transition from a conformationally disordered to a conformationally ordered state as the temperature is lowered. The phase transition occurs ca. 11 °C above the bulk melting point of tetradecane. A new experimental arrangement is described for acquiring SF spectra from surfactants at the oil-water interface. The key features of this approach are the stabilisation of a thin oil film between a sapphire prism and an aqueous phase, and the use of total internal reflection to enhance the total signal and discriminate against signals from other interfaces in the system. With this new methodology, the first SF vibrational spectra of surfactant monolayers at an alkane-water interface were obtained. Surface tensiometry was used to characterise the monolayers further. The structure of CTAB monolayers at the hexadecane-water interface was determined by SFS and compared with monolayers of CTAB at the air-water interface. At low concentrations, CTAB/hexadecane showed the expected features in the C-H stretching region, characteristic of a conformationally disordered monolayer. As the bulk concentration approached the critical micelle concentration, the spectra changed to one characteristic of a more ordered, upright conformation. Ellipsometric measurements supported this conclusion. This qualitative structural change is not observed in analogous monolayers at the air-water interface or CCl₄-water interface, or in surfactant solutions in contact with a hydrophobic solid surface.

This thesis presents a mathematical model of the nanoporous anode within a dyesensitised solar cell (DSC). The main purpose of this work is to investigate interfacial charge transfer and charge transport within the porous anode of the DSC under both illuminated and non-illuminated conditions. Within the porous anode we consider many of the charge transfer reactions associated with the electrolyte species, adsorbed dye molecules and semiconductor electrons at the semiconductor-dye- electrolyte interface. Each reaction at this interface is modelled explicitly via an electrochemical equation, resulting in an interfacial model that consists of a coupled system of non-linear algebraic equations. We develop a general model framework for charge transfer at the semiconductor-dye-electrolyte interface and simplify this framework to produce a model based on the available interfacial kinetic data. We account for the charge transport mechanisms within the porous semiconductor and the electrolyte filled pores that constitute the anode of the DSC, through a one- dimensional model developed under steady-state conditions. The governing transport equations account for the diffusion and migration of charge species within the porous anode. The transport model consists of a coupled system of non-linear differential equations, and is coupled to the interfacial model via reaction terms within the mass-flux balance equations. An equivalent circuit model is developed to account for those components of the DSC not explicitly included in the mathematical model of the anode. To obtain solutions for our DSC mathematical model we develop code in FORTRAN for the numerical simulation of the governing equations. We additionally employ regular perturbation analysis to obtain analytic approximations to the solutions of the interfacial charge transfer model. These approximations facilitate a reduction in computation time for the coupled mathematical model with no significant loss of accuracy. To obtain predictions of the current generated by the cell we source kinetic and transport parameter values from the literature and from experimental measurements associated with the DSC commissioned for this study. The model solutions we obtain with these values correspond very favourably with experimental data measured from standard DSC configurations consisting of titanium dioxide porous films with iodide/triiodide redox couples within the electrolyte. The mathematical model within this thesis enables thorough investigation of the interfacial reactions and charge transport within the DSC.We investigate the effects of modified cell configurations on the efficiency of the cell by varying associated parameter values in our model. We find, given our model and the DSC configuration investigated, that the efficiency of the DSC is improved with increasing electron diffusion, decreasing internal resistances and with decreasing dark current. We conclude that transport within the electrolyte, as described by the model, appears to have no limiting effect on the current predicted by the model until large positive voltages. Additionally, we observe that the ultrafast injection from the excited dye molecules limits the interfacial reactions that affect the DSC current.

Made available in DSpace on 2014-12-17T14:16:25Z (GMT). No. of bitstreams: 1 AcariliaES_Dissert_01.pdf: 1640327 bytes, checksum: 9c4568aff953d538d26000691eb0407d (MD5) Previous issue date: 2009-03-10 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Colon-specific drug delivery systems have attracted increasing attention from the pharmaceutical industry due to their ability of treating intestinal bowel diseases (IBD), which represent a public health problem in several countries. In spite of being considered a quite effective molecule for the treatment of IBD, mesalazine (5-ASA) is rapidly absorbed in the upper gastrointestinal tract and its systemic absorption leads to risks of adverse effects. The aim of this work was to develop a microparticulate system based on xylan and Eudragit? S- 100 (ES100) for colon-specific delivery of 5-ASA and evaluate the interaction between the polymers present in the systems. Additionaly, the physicochemical and rheological properties of xylan were also evaluated. Initially, xylan was extracted from corn cobs and characterized regarding the yield and rheological properties. Afterwards, 10 formulations were prepared in different xylan and ES100 weight ratios by spray-drying the polymer solutions in 0.6N NaOH and phosphate buffer pH 7.4. In addition, 3 formulations consisting of xylan microcapsules were produced by interfacial cross-linking polymerization and coated by ES100 by means of spray-drying in different polymer weight ratios of xylan and ES100. The microparticles were characterized regarding yield, morphology, homogeneity, visual aspect, crystallinity and thermal behavior. The polymer interaction was investigated by infrared spectroscopy. The extracted xylan was presented as a very fine and yellowish powder, with mean particle size smaller than 40μm. Regarding the rheological properties of xylan, they demonstrated that this polymer has a poor flow, low density and high cohesiveness. The microparticles obtained were shown to be spherical and aggregates could not be observed. They were found to present amorphous structure and have a very high thermal stability. The yield varied according to the polymer ratios. Moreover, it was confirmed that the interaction between xylan and ES100 occurs only by means of physical aggregation / Sistemas c?lon-espec?ficos t?m atra?do o interesse da ind?stria farmac?utica devido ? possibilidade de tratarem enfermidades, como as doen?as inflamat?rias intestinais (DII), que compreendem um problema de sa?de p?blica em muitos pa?ses. Apesar de ser considerada uma mol?cula bastante eficiente para o tratamento das DII, a mesalazina (5-ASA) ? rapidamente absorvida no trato gastrintestinal superior e sua absor??o sist?mica leva ? incid?ncia de s?rios efeitos adversos. Este trabalho teve como objetivos produzir um sistema polim?rico microparticulado ? base de xilana e Eudragit? S-100 (ES100) para libera??o c?lon-espec?fica de 5-ASA e avaliar a intera??o entre os pol?meros constituintes do sistema, al?m de aprofundar a caracteriza??o f?sico-qu?mica e tecnol?gica da xilana. A xilana foi extra?da a partir de sabugos de milho e caracterizada quanto ao rendimento, granulometria, cristalinidade, propriedades reol?gicas e comportamento t?rmico. Em seguida, 10 formula??es contendo 5-ASA foram preparadas em diferentes propor??es de xilana e ES100 atrav?s da secagem por aspers?o das solu??es polim?ricas com NaOH 0,6N ou tamp?o-fosfato pH 7,4, como solvente. Al?m disso, 3 formula??es constitu?das de microc?psulas de xilana produzidas por reticula??o polim?rica interfacial foram revestidas por ES100 atrav?s de secagem por aspers?o em diferentes propor??es polim?ricas e empregando-se NaOH 0,6N ou tamp?o-fosfato pH 7,4, como solvente. As micropart?culas foram avaliadas quanto ao rendimento, morfologia, granulometria, homogeneidade, aspecto visual, cristalinidade e comportamento t?rmico. A intera??o entre os pol?meros foi investigada atrav?s da espectroscopia na regi?o do infravermelho e de an?lises t?rmicas. A xilana extra?da apresentou-se como um p? muito fino, com tamanho m?dio inferior a 40μm, e com colora??o opaca levemente amarelada. A avalia??o das propriedades reol?gicas da xilana permitiram a caracteriza??o desse pol?mero, em seu estado original de p?, como um material de baixa densidade, fluxo restrito e bastante coesivo. Foram obtidas micropart?culas esf?ricas e sem presen?a de agregados, com estrutura amorfa, em sua maior parte, e bastate est?veis a temperaturas elevadas. Al?m disso, confirmou-se que a intera??o entre xilana e ES100 ocorre apenas por agrega??o f?sica

L’utilisation de composites à matrice thermodurcissable et fibres continues est en constante progression dans le secteur aéronautique, ferroviaire, et automobile. Afin d’améliorer les composites obtenus, notamment leur résistance à l’impact et leur conductivité électrique, des nanocharges organiques ou inorganiques peuvent être ajoutées. Les nanotubes de carbone (CNT) font partie des candidats les plus prometteurs pour le renforcement de composites à multi-échelle. Cependant, il s’avère difficile de contrôler la dispersion, la répartition et l’orientation des CNT, après les avoir mélangés aux prépolymères. Une nouvelle stratégie d’insertion des CNT dans un composite consiste à combiner des fibres de CNT avec des fibres de carbone. L’orientation et l’organisation structurelle des CNT au sein de la fibre permettent d’obtenir d’excellentes propriétés mécaniques et électriques. Dans notre étude, les propriétés de fibres contenant exclusivement des CNT, obtenues par direct spinning, ont été comparées à celles de fibres de carbone (non-ensimées, ensimées, et CNT en surface). Différentes interfaces entre les fibres de CNT, fibres de carbone et deux types de matrices époxy (de TG très différentes) ont été générées et testées par des essais de fragmentation de fibre dans la matrice. La contrainte de cisaillement interfaciale fibre/matrice a été évaluée afin de déterminer l’influence des diverses fibres et ensimages sur les performances mécaniques de composites à matrice organique et à fibres continues. En outre, la nature de l’adhésion et la qualité de l’interphase entre la matrice et la fibre ont été caractérisées par plusieurs techniques d’analyses et d’observations à multi-échelles. / Nowadays, polymer-matrix composites reinforced with carbon fibers are increasingly used in the whole transport sector (aerospace, automotive and railway industries). However, the obtained parts still suffer from low impact resistance and low damage tolerance. To improve these properties, the matrix precursors have to be combined with organic or inorganic compounds to lead to multi-phased matrices. Among them, carbon nanotubes (CNT) are especially promising for targeting multi-scale reinforcement. Since high quality of the parts are required, continuous-fibers-reinforced composites can be produced by resin transfer molding (RTM) which also offers a reduced cost if compared with high temperature- and high pressure-based processes. However, RTM requires a very low viscosity of the polymer precursors and CNT-filled precursors are far too viscous to be injected on dry performs. In addition, this strategy does not allow for a control of the CNT location and orientation in the final part. In this study, innovative ways have been developed to insert CNT in the preform with local positioning and defined orientation. Deliveries of CNT in the matrix, from a neat carbon multi-nanotubes fiber produced by direct spinning, or from a CNT grown on carbon fiber were investigated in two types of epoxy matrices (with very different TG). Different polymer matrix/fiber interfaces have been generated using neat carbon multi-nanotubes fiber, CNT grown on carbon fiber and conventional carbon fiber, with or without sizing. A fine mechanical characterization of various fibers and particularly the measurement of single fiber interfacial properties have been performed in order to determine mechanical performance of continuous fiber reinforced composites. In addition, the nature of adhesion and quality of matrix/fiber interface have been fully evaluated by different multi-scale analyses and suitable microstructural observations.