L’incorporation de fibres de carbone greffées avec des nanotubes de carbone (CNTs-CF) dansune matrice polymère permet d’obtenir des matériaux avec des propriétés mécaniques, des propriétés de conductivité électrique et de conductivité thermique notamment améliorées. Ces matériaux sont des candidats idéaux pour être intégrés dans des applications fonctionnelles et même structurales dans les domaines de l’industrie aéronautique, de l’industrie automobile, de la défense et de l’industrie des produits pour le sport. L’objectif (des travaux menés au cours) de cette thèse de Doctorat est d’établir une technique efficace de production de matériaux composites possédant des propriétés multifonctionnelles. Nous étudions l’adaptation d’une technique de dépôt de polymère par plasma sur la surface de fibres de carbone (CFs) puis sur la surface de CNT-CFs. Le dépôt de polymère par plasma sur la surface CNT-CFs est ici recherché non pour des raisons de sécurité, certainement avantageuses, mais pour conférer les propriétés des nanotubes de carbone à l’ensemble du matériau composite. Dans le premier chapitre, nous proposons un tour d’horizon des 2 sujets majeurs de notre étude : (1) les matériaux composites et leurs applications (2) les applications des plasmas pour procédés de traitement des matériaux. Dans le deuxième chapitre, nous présentons la procédure expérimentale du traitement plasma des fibres, ainsi que le schéma détaillé du mécanisme permettant de manipuler les échantillons. Nous précisons aussi les procédures suivies pour la caractérisation chimique, électrique et mécanique des fibres et des matériaux composites. Dans le troisième chapitre, nous évaluons les effets des variations de 2 et de 3 paramètres (par exemple la puissance plasma utilisée, la durée d’exposition et la nature des précurseurs) sur la résistivité électrique des fibres de carbone (CFs) et des fibres de carbone greffées de nanotubes de carbone (CNTs-CF) par la méthodologie des surfaces de réponse. D’après cette étude pour l’optimisation du procédé, nous étudions les principaux facteurs et les interactions entre les différents paramètres. Nous montrons les variables (ou facteurs) qui ont la plus grande influence sur la résistivité électrique sur les 2 types de fibres de carbone. Dans le quatrième chapitre, nous traitons des études de caractérisations des fibres de carbone par XPS (composition chimique), MEB (microstructure), AFM (topologie, rugosité) et TGA (stabilité thermique, cinétique de dégradation). Il s’agit de fournir une meilleure compréhension des structures obtenues sur de telles fibres dans des domaines allant du macroscopique jusqu’au niveau de l’atome. Nous analysons aussi des échantillons avant traitement pour comparer les différences morphologiques et chimiques avec les échantillons traités par plasma. Finalement, dans le cinqième chapitre, nous étudions les proprieties mécaniques et électriques des échantillons de matériaux composites élaborés à partir de fibres non-traitées et des fibres traitées par dépôt plasma de polypyrrole (sur CFs et CNTs-CF). A partir des essais mécaniques et des mesures électriques, nous concluons sur les améliorations apportées par le traitement plasma. / The incorporation of carbon nanotubes grafted carbon fibers (CNTs-CF) into polymermatrices provides highly-enhanced mechanical, electrical, and thermal properties to the materials. They are ideal candidates to be integrated into structural and functional applications in the fields of aerospace, automobile, defense, and sport industries. The aim of this PhD thesis is to establish an efficient technique to produce carbon fiber composites with multifunctional properties. We study the adaptation of a plasma technique for polymer deposition on the surface of carbon fibers (CFs) and carbon nanotubes grafted carbon fibers (CNTs-CF). The plasma polymer deposition on CNTs-CF is not performed only to keep nanotubes on the carbon fiber surface for safety reasons, but it is also applied to retain the bulk properties of those materials. In the first chapter, we give an overview of the two major subjects of the study: (1) composites and their applications, (2) plasma application for materials processing. In the second chapter, we present the experimental procedure of the plasma treatment process of fibers including the detailed design of the plasma system for the treatment of these samples. Then we explain the procedures of several sorts of characterization studies of fibers and composites (e.g. chemical, electrical, and mechanical). In the third chapter, we evaluate the effect of double and triple varied process parameters (i.e. plasma power, exposure time and precursors) on electrical resistivity of CFs and CNTs-CF by response surface methodology. According to the optimization studies we investigate the main factors and the interactions between the different process parameters and we demonstrate which variable (or factor) has the greatest effect on the electrical resistivity of both types of the treated carbon fibers. In the forth chapter, we deal with the characterization studies of the plasma treated CFs and CNTs-CF by using XPS (chemical structure), SEM (microstructure), AFM (topography, roughness), and TGA (thermal stability, degradation kinetics) in order to provide better understanding of the obtained structures on such fibers in a domain ranging from macroscopic to atomic scales. We also analyze the untreated samples to compare mainly the chemical and morphological differences between unmodified and plasma modified fibers. Finally, in the fifth chapter, we study the mechanical and electrical properties of untreated and plasma polypyrrole treated CFs and CNTs-CF reinforced composites experimentally. According to the electrical and mechanical tests, we determine the healing effect of plasma surface treatment performed on CFs and CNTs-CF.

Carbon fiber-reinforced plastics (CFRPs) have gained widespread popularity as a lightweight, high-strength alternative to traditional materials. The unique anisotropic properties of CFRP make processing difficult, especially using conventional methods. This study investigates laser cutting by ablation as an alternative by comparing two near-infrared laser systems to a typical mechanical machining process. This research has potential applications in the automotive and aerospace industries, where CFRPs are particularly desirable for weight savings and fuel efficiency. First, a CNC mill was used to study the effects of process parameters and tool design on machining quality. Despite high productivity and flexible tooling, mechanical drilling suffers from machining defects that could compromise structural performance of a CFRP component. Rotational feed rate was shown to be the primary factor in determining the axial thrust force, which correlated with the extent of delamination and peeling. Experimental results concluded that machining quality could be improved using a non-contact laser-based material removal mechanism. Laser machining was investigated first with a Yb:YAG fiber laser system, operated in either continuous wave or pulse-modulated mode, for both cross-ply and woven CFRP. For the first time, energy density was used as a control variable to account for changes in process parameters, predicting a logarithmic relationship with machining results attributable to plasma shielding effects. Relevant process parameters included operation mode, laser power, pulse overlap, and cross-ply surface fiber orientation, all of which showed a significant impact on single-pass machining quality. High pulse frequency was required to successfully ablate woven CFRP at the weave boundaries, possibly due to matrix absorption dynamics. Overall, the Yb:YAG fiber laser system showed improved performance over mechanical machining. However, microsecond pulses cause extensive thermal damage and low ablation rates due to long laser-material interaction time and low power intensity. Next, laser machining was investigated using a high-energy nanosecond-pulsed Nd:YAG NIR laser operating in either Q-Switch or Long Pulse mode. This research demonstrates for the first time that keyhole-mode cutting can be achieved for CFRP materials using a high-energy nanosecond laser with long-duration pulsing. It is also shown that short-duration Q-Switch mode results in an ineffective cutting performance for CFRP, likely due to laser-induced optical breakdown. At sufficiently high power intensity, it is hypothesized that the resulting plasma absorbs a significant portion of the incoming laser energy by the inverse Bremsstrahlung mechanism. In Long Pulse mode, multi-pass line and contour cutting experiments are further performed to investigate the effect of laser processing parameters on thermal damage and machined surface integrity. A logarithmic trend was observed for machining results, attributable to plasma shielding similar to microsecond fiber laser results. Cutting depth data was used to estimate the ablation threshold of Hexcel IM7 and AS4 fiber types. Drilling results show that a 2.2 mm thick cross-ply CFRP panel can be cut through using about 6 laser passes, and a high-quality machined surface can be produced with a limited heat-affected zone and little fiber pull-out using inert assist gas. In general, high-energy Long Pulse laser machining achieved superior performance due to shorter pulse duration and higher power intensity, resulting in significantly higher ablation rates. The successful outcomes from this work provide the key to enable an efficient high-quality laser machining process for CFRP materials.

[pt] O reforço de estruturas de concreto armado torna-se necessário por uma série de fatores, tais como: erros de projeto ou de execução que levam a sistemas estruturais inseguros; deterioração do concreto e do aço causada por envelhecimento natural; agentes agressivos ou acidentes como incêndio e choques; mudança no tipo de utilização original da estrutura através do aumento do carregamento e/ou modificações na sua geometria. A aplicação de compósitos de fibra de carbono para reforço de estruturas de concreto armado representa o que há de mais moderno em engenharia estrutural. O uso deste material é bastante interessante devido à sua leveza, alta resistência mecânica, resistência à corrosão, neutralidade eletromagnética, fácil aplicação e manutenção das dimensões originais do elemento estrutural. A escolha deste tipo de reforço, em vez de sistemas tradicionais que utilizam chapas de aço, depende da viabilidade econômica e de restrições específicas feitas no projeto. O objetivo deste trabalho é desenvolver um modelo analítico para o dimensionamento à flexão de vigas de concreto armado reforçadas com compósitos de fibras de carbono. Foi realizada uma revisão da literatura disponível de modo a se obter evidências experimentais acerca do assunto. Com o propósito de avaliar a eficiência do modelo analítico desenvolvido, os resultados numéricos calculados com este modelo são discutidos e comparados com os resultados experimentais e teóricos obtidos da literatura. / [en] The strengthening of reinforced concrete structures turns to be necessary due to a number of factors, such as: mistakes in the design or in the construction leading to unsafe structural systems; deterioration of concrete and steel caused by natural aging, aggressive agents or accidents like fire and shocks; the changing of the original use of the structure with the increase of loading and/or modifications in the geometry. The application of carbon fiber composites for strengthening of reinforced concrete structures is a very new and modern issue in structural engineering. The use of this material is very interesting due to its lightness, high mechanical strength, resistance to corrosion, electromagnetic neutrality, easy application and maintenance of the original shape of the structural element. The choice of this type of reinforcement, instead of more traditional systems using steel plates, depends on the economical viability and specific restrictions made in the project. The objective of this work is to develop analytical model for flexural design of reinforced concrete beams strengthened with carbon fiber composites. A literature review was carried out in order to obtain the experimental evidences on this subject. In order to evaluate the efficiency of the analytical model, the numerical results obtained with this model are discussed and compared with the experimental and numerical results obtained from literature.

Within the framework of this thesis, three innovative electrochemical devices have been studied. A part of the work is devoted to an already existing device, laminates which are debonded by the application of a voltage. This type of material can potentially be used in a wide range of applications, including adhesive joints in vehicles to both reduce the total weight and to simplify the disassembly after end-of-life, enabling an inexpensive recycling process. Although already a functioning device, the development and tailoring of this process was slowed by a lack of knowledge concerning the actual electrochemical processes responsible for the debonding. The laminate studied consisted of an epoxy adhesive, mixed with an ionic liquid, bonding two aluminium foils. The results showed that the electrochemical reaction taking place at the releasing anode interface caused a very large increase in potential during galvanostatic polarization. Scanning electron microscopy images showed reaction products growing out from the electrode surface into the adhesive. These reaction products were believed to cause the debonding through swelling of the anodic interface so rupturing the adhesive bond. The other part of the work in this thesis was aimed at innovative lithium ion (Li‑ion) battery concepts. Commercial Li-ion batteries are two-dimensional thin film constructions utilized in most often mechanically rigid products. Two routes were followed in this thesis. In the first, the aim was flexible batteries that could be used in applications such as bendable reading devices. For this purpose, nano-fibrillated cellulose was used as binder material to make flexible battery components. This was achieved through a water-based filtration process, creating flexible and strong papers. These paper-based battery components showed good mechanical properties as well as good rate capabilities during cycling. The drawback using this method was relatively low coulombic efficiencies believed to originate from side-reactions caused by water remnants in the cellulose structure. The second Li-ion battery route comprised an electrochemical process to coat carbon fibers, shown to perform well as negative electrode in Li-ion batteries, from a monomer solution. The resulting polymer coatings were ~500 nm thick and contained lithium ions. This process could be controlled by mainly salt content in the monomer solution and polarization time, yielding thin and apparently pin-hole free coatings. By utilizing the carbon fiber/polymer composite as integrated electrode and electrolyte, a variety of battery designs could possibly be created, such as three-dimensional batteries and structural batteries. / <p>QC 20130403</p>

Composites have been developed with great success by the use of fiber reinforcements in metallic materials. Fiber reinforced metal matrices possess great potential to be the next generation of advanced composites offering many advantages compared to fiber reinforced polymers. Specific advantages include high temperature capability, superior environmental stability, better transverse modulus, shear and fatigue properties. Although many Metal Matrix Composites (MMCs) are attractive for use in different industrial applications, Aluminium Matrix Composites (AMCs) are the most used in advanced applications because they combine acceptable strength, low density, durability, machinability, availability, effectiveness and cost. The present study focuses on the fabrication of aluminium matrix composite plates by squeeze casting using plain weave carbon fiber preform (AS4 Hexcel) as reinforcement and a matrix of wrought aluminium alloy 1235-H19. The objective is to investigate the process feasibility and resulting materials properties such as hardness at macro- and micro-scale, impact and bend strength. The properties obtained are compared with those of 6061/1235-H19 aluminium plates that were manufactured under the same fabrication conditions. The effect of fiber volume fraction on the properties is also investigated. Furthermore, the characterization of the microstructure is done using Optical Microscopy (OM) and Scanning Electron Microscopy (SEM) in order to establish relationships between the quality of the fiber/aluminium interface bond and mechanical properties of the composites. In conclusion, aluminium matrix composite laminate plates were successfully produced. The composites show a good chemical bond between the fiber and the aluminium matrix. This bond resulted from heterogeneous precipitation of aluminium carbides (Al4C3) at the interface between aluminium matrix and carbon fiber. The hardness at macro- and micro-scale of the composites increases by over 50% and the flexural modulus increases by about 55%. The toughness of the composite decreases due to the presence of brittle phases which can be improved by better oxidation prevention. Also, an optimal carbon volume fraction was observed that provides optimal properties including peak hardness, peak stiffness and peak toughness.

Metallic robotic arms, or manipulators, currently dominate automated industrial operations, but due to their intrinsic weight, have limited usefulness for large-scale applications in terms of precision, speed, and repeatability. This thesis focuses on exploring the feasibility of using polymeric composite materials for the construction of long-reach robotic arms. Different manipulator layouts were investigated and an ideal design was selected for a robotic arm that has a 5 [m] reach, 50 [kg] payload, and is intended to operate on large objects with complex curvature. The cross-sectional geometry of the links of the arm were analyzed for optimal stiffness- and strength-to-weight ratios that are capable of preserving high precision and repeatability under time-dependent external excitations. The results lead to a novel multi-segment link design and method of production. A proof-of-concept prototype of a two degrees-of-freedom (2-DOF) robotic arm with a reach of 1.75 [m] was developed. Both static and repeatability testing were performed for verification. The results indicated that the prototype robot main-arm constructed of carbon fiber-epoxy composite material provides good stiffness-to-weight and strength-to-weight ratios. Finite element analysis (FEA) was performed on a 3-D computer model of the arm. Successful verification led to the use of the 3-D model to define the dimensions of an industrial-sized robotic arm. The results obtained indicate high stiffness and minimal deflection while achieving a significant weight reduction when compared to commercial arms of the same size and capability.

In this thesis, a long-term operation direct methanol fuel cell (DMFC) stack is developed. In order to reach this goal required in many ways, including select highly chemical stability materials, operating conditions must also be stable, and avoid changing the MEA structure when preserved, then can cause the DMFC to maintain stable operation for a long time. First of all, in order to avoid contaminating electrode, this study find out the chemical instability materials. Second, this study design a device which does not require power then can stability supply consumption fuel, and apply this device in 16-cell DMFC. Finally compare with continuous fuel supply and without fuel supply, two operating conditions performance stability. From these experiments can find out, the DMFC indeed in stable operation for a long time under the appropriate supplement. Traditional fuel supply systems typically using the pump fuel recycling, so the structure is more complex, difficult to reduce the volume, and not conducive to carry. If using a passive operation, fuel completely stored in the reaction Chamber, even though the structure is simple there will be a problem with fuel supply. In recent years, someone use vapors of methanol to supply the fuel, although can use high concentration methanol to extend operating time, but the evaporation rate is difficult to control, the fuel can¡¦t be supplied in time, especially when the large current is needed, and CROSSOVER issues would be difficult to overcome. In our 16-cell DMFC, continues to add appropriate amount of fuel consumed which according to the different current. The fuel supply device with a sliding control plate which can control methanol and water diffusion rate respectively. This device only to provide consumed by reaction and leaked fuel in anode chamber, so that the methanol concentration can maintained in the proper range at anode chamber. This device only use diffusion and gravity effects, don't use a fuel pump, so will not consume DMFC power.

¡@¡@In this thesis, we develop a self-humidifying PEMFC. The humidifying effects on the stability and impedance of the fuel cell are studied. A portable and passive PEMFC stack usually exposes in the ambient no matter that it works or not. However, the ambient is far from saturated. The water within MEA will diffuse to the membrane¡¦s surface and evaporate continuously. The membrane will be short in water without water supplying. Because the conductivity of H+ of the membrane is highly dependent on water content, the dehydration of the membrane will reduce the interconnected passageway of H+ and affect the performance of fuel cell directly. And because of the different expansion rate the electrode of MEA is also possible to separate from its membrane when it operates repeatedly. This separation will make the performance of fuel cell an unrecovered decay. ¡@¡@At first, the hydration status of the dry membrane is observed. We measure the addition weight of water into membrane by using cotton thread humidifying, and estimate the water permeation distances. The maximum water supply rate of cotton thread is 4.26mg/min, and the permeation rate of water through membrane where is 2.5cm from water surface is 0.15mg/cm¡Dmin. Then we design the self-humidifying devices of PEMFC stack. The humidifying effects on performance and stability of the fuel cell are studied. ¡@¡@When the active area is 0.7¡Ñ4.5cm2 and the cotton thread is 5mm from the center of electrode the supplying water can arrive at the reaction area under the electrode through the membrane in one minute. The difference of the supplying water between the bottom and top is 7% by using 6cm cotton thread. Therefore water can hydrate the membrane and the difference of the supplying water between bottom and top is not oversize. The higher current load, the voltage efficiency is lower. The increasing heat generation rate results in the water evaporation rate would be greater than the water generation rate. So the drop of voltage under higher current is greater than lower current. By comparing with the difference of high frequency impedance the change of humidifying is smaller between 1hr operating. It indicates that humidifying by cotton thread keeps the membrane hydration.

This study has two purposes: First, the catalyst-coated membrane (CCM) method to produce high performance and high utilization of electrode, and the other is to enhance the fuel cell performance with the heterogeneous carbon fiber bunch framework of stack. First, to establish an ideal electrode structure, there has an intensive triple phase boundaries. We will describe how the procedure of reliable and practical electrode improved following the optimization of (1) the spray system, and (2) the catalyst dispersion. We will also focus (3) modification of the spray system, and (4) electrode performance analysis. In addition, investigate of the single cell performance in heterogeneous carbon fiber bunch framework. We will find that: (1) Increasing the catalyst loading and concentrated the catalyst activation reaction, can be improve the electrode performance and catalyst utilization. (2) Coating a thin conductive layer onto membrane electrode (ME), be a precise hot-pressue process in the Stack and MEA or GDL and ME, can be reduce the contact resistance. Specially, reduce the carbon fiber coverage fraction with electrode area, result the activation reaction decay and ohmic loss obviously. (3) Increasing the gas flow rate, can enhance the mass transfer performance, but increase the pressure of the reaction gas, can¡¦t significant effect on performance. Besides, when the stack is anode side up, seems favorable to the exclusion the generate water of cathode.

Abstract A one-watt portable air-breathing direct methanol fuel cell stack (called DMFC), which can supply fuel passively and operate steadily, is developed in this thesis. A DMFC to maintain its performance stable, the most important strategy is to keep the methanol concentration in reacting chamber to be proper and stable. A fuel supplying system will be in accordance with the depletion of chemical reaction and the leakage of fuel under different circuit current to supplying fuel. To regulate the methanol and water supplying, a fuel supplying system by gravitation and diffusion forces deliver methanol and water to fill up the consumed fuel to maintain the concentration of methanol solution in anode reaction chamber, by adjusting a sliding gate to control the area of a diffusive membrane and utilizing three cotton threads and hoses to distribute the fuel to proper location. In doing so, the methanol concentration in the anode chamber can keep within an appropriate range, so that the DMFC stack can operate stably for a longer period. Yet the diffusivity of the diffusive membrane is comparatively less, the supply system is not easy to downsize. To reduce the size of portable DMFC, we make use of a fuel plug tank to combine the supply tank and reacting chamber, and thus the cell package is more portable. Between the plug tank and the reacting chamber, the three cotton threads are used to distribute the fuel to proper location. The above two design with no extra auxiliary device; therefore, no extra energy will be consumed. To reduce the fuel leakage, and make more use of fuel, four block films is pasted on the bare area of the nafion membranes in a 16-cell DMFC stack. If no fuel is fed into reaction chamber, this will prolong the cell operation time. Under the condition of 3.7 V (cell phone rated voltage) and the operating current 225 mA, our experiments display that the stacks with the two fuel supplying systems can continuously operate for more than 3 hours with no obvious change in methanol concentration within reaction chamber. The experimental results show that this simple passive fuel supplemental system can really keep the DMFC stack operating stably for a sufficient long period.