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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

Matrix-dominated constitutive laws for composite materials

He, Yihong 06 July 2010 (has links)
Accurate three-dimensional stress-strain constitutive properties are essential to understanding complex deformation and failure mechanisms for materials with highly anisotropic mechanical properties. The large number of different methods and specimen types currently required to generate three-dimensional allowables for structural design slow down the material characterization. Also, some of the material constitutive properties are never measured due to prohibitive cost of the specimens needed. A method for measurement of three-dimensional constitutive properties using short-beam specimens subject to three-point bend load has been recently developed. This method is based on the Digital Image Correlation (DIC) full-field deformation measurement and closed-form stress approximation. The purpose of this work is to improve the accuracy of the constitutive properties through accurate stress solution. A method is developed based on a combination of full-field strain measurement and nonlinear finite element stress analysis in the material characterization. The nonlinear shear stress-strain relations are the major concern in this work. An iterative procedure is applied to update the nonlinear shear properties using iterative finite element simulations. The accuracy of the numerical procedure is verified by comparing the finite element strain results with full-field measurements. The procedure is further verified using the V-notched beam test results. Excellent agreement has been achieved in the verification. Simplicity of the short-beam specimens and accuracy of the constitutive property approximations make the present method attractive for measurement of three-dimensional stress-strain relations for anisotropic materials at various load rates.
72

Salts as highly diverse porogens : functional ionic liquid-derived carbons and carbon-based composites for energy-related applications

Fechler, Nina January 2012 (has links)
The present thesis is to be brought into line with the current need for alternative and sustainable approaches toward energy management and materials design. In this context, carbon in particular has become the material of choice in many fields such as energy conversion and storage. Herein, three main topics are covered: 1)An alternative synthesis strategy toward highly porous functional carbons with tunable porosity using ordinary salts as porogen (denoted as “salt templating”) 2)The one-pot synthesis of porous metal nitride containing functional carbon composites 3)The combination of both approaches, enabling the generation of highly porous composites with finely tunable properties All approaches have in common that they are based on the utilization of ionic liquids, salts which are liquid below 100 °C, as precursors. Just recently, ionic liquids were shown to be versatile precursors for the generation of heteroatom-doped carbons since the liquid state and a negligible vapor pressure are highly advantageous properties. However, in most cases the products do not possess any porosity which is essential for many applications. In the first part, “salt templating”, the utilization of salts as diverse and sustainable porogens, is introduced. Exemplarily shown for ionic liquid derived nitrogen- and nitrogen-boron-co-doped carbons, the control of the porosity and morphology on the nanometer scale by salt templating is presented. The studies within this thesis were conducted with the ionic liquids 1-Butyl-3-methyl-pyridinium dicyanamide (Bmp-dca), 1-Ethyl-3-methyl-imidazolium dicyanamide (Emim-dca) and 1 Ethyl 3-methyl-imidazolium tetracyanoborate (Emim-tcb). The materials are generated through thermal treatment of precursor mixtures containing one of the ionic liquids and a porogen salt. By simple removal of the non-carbonizable template salt with water, functional graphitic carbons with pore sizes ranging from micro- to mesoporous and surface areas up to 2000 m2g-1 are obtained. The carbon morphologies, which presumably originate from different onsets of demixing, mainly depend on the nature of the porogen salt whereas the nature of the ionic liquid plays a minor role. Thus, a structural effect of the porogen salt rather than activation can be assumed. This offers an alternative to conventional activation and templating methods, enabling to avoid multiple-step and energy-consuming synthesis pathways as well as employment of hazardous chemicals for the template removal. The composition of the carbons can be altered via the heat-treatment procedure, thus at lower synthesis temperatures rather polymeric carbonaceous materials with a high degree of functional groups and high surface areas are accessible. First results suggest the suitability of the materials for CO2 utilization. In order to further illustrate the potential of ionic liquids as carbon precursors and to expand the class of carbons which can be obtained, the ionic liquid 1-Ethyl-3-methyl-imidazolium thiocyanate (Emim-scn) is introduced for the generation of nitrogen-sulfur-co-doped carbons in combination with the already studied ionic liquids Bmp-dca and Emim-dca. Here, the salt templating approach should also be applicable eventually further illustrating the potential of salt templating, too. In the second part, a one-pot and template-free synthesis approach toward inherently porous metal nitride nanoparticle containing nitrogen-doped carbon composites is presented. Since ionic liquids also offer outstanding solubility properties, the materials can be generated through the carbonization of homogeneous solutions of an ionic liquid acting as nitrogen as well as carbon source and the respective metal precursor. The metal content and surface area are easily tunable via the initial metal precursor amount. Furthermore, it is also possible to synthesize composites with ternary nitride nanoparticles whose composition is adjustable by the metal ratio in the precursor solution. Finally, both approaches are combined into salt templating of the one-pot composites. This opens the way to the one-step synthesis of composites with tunable composition, particle size as well as precisely controllable porosity and morphology. Thereby, common synthesis strategies where the product composition is often negatively affected by the template removal procedure can be avoided. The composites are further shown to be suitable as electrodes for supercapacitors. Here, different properties such as porosity, metal content and particle size are investigated and discussed with respect to their influence on the energy storage performance. Because a variety of ionic liquids, metal precursors and salts can be combined and a simple closed-loop process including salt recycling is imaginable, the approaches present a promising platform toward sustainable materials design. / Die vorliegende Arbeit basiert auf der Notwendigkeit für eine alternative und nachhaltige Energiewirtschaft sowie alternativer Herstellungsmethoden der damit verbundenen Materialien. Hierbei kommt besonders Kohlenstoffen und kohlenstoffbasierten Systemen eine hohe Bedeutung zu. Im Rahmen der Dissertation wurden drei Ansätze verfolgt, die zu der Entwicklung alternativer Strategien zur Herstellung poröser Heteroatom-enthaltender Kohlenstoffe und deren Komposite beitragen. Die Materialien wurden des Weiteren für die CO2 Nutzung sowie Energiespeicherung in Form von Superkondensatoren getestet. Allen Materialien ist gemeinsam, dass sie ausgehend von ionischen Flüssigkeiten, Salze mit einem Schmelzpunkt unterhalb von 100 °C, als Kohlenstoffvorstufe durch Hochtemperaturverfahren hergestellt wurden. Im ersten Teil wird ein alternatives und nachhaltiges Verfahren zur Herstellung hochporöser Stickstoff und Stickstoff-Bor-haltiger Kohlenstoffe vorgestellt. Bei dieser als „Salztemplatierung“ bezeichneten Methode werden herkömmliche Salze als Porogen verwendet. Damit sind sehr hohe Oberflächen erreichbar, die neben der Porengröße und dem Porenvolumen durch die Variation der Salzspezies und Salzmenge einstellbar sind. Dies bietet gegenüber herkömmlichen Templatierungsverfahren den Vorteil, dass das Salz nach erfolgter Karbonisierung der ionischen Flüssigkeit in Anwesenheit der nicht karbonisierbaren Salzspezies einfach mit Wasser auswaschbar ist. Hierbei ist ein Recyclingprozess denkbar. Bei hohen Synthesetemperaturen werden graphitische, bei niedrigen hochfunktionalisierte, polymerartige Produkte erhalten. Letztere erwiesen sich als vielversprechende Materialien für die CO2 Nutzung. Unter Verwendung einer bisher nicht eingesetzten ionische Flüssigkeit konnte weiterhin die Einführung von Schwefel als Heteroatom ermöglicht werden. Im zweiten Teil wird eine Templat-freie Einschrittsynthese von porösen Kompositen aus Metallnitrid Nanopartikeln und Stickstoff-dotiertem Kohlenstoff vorgestellt. Die Materialien werden ausgehend von einer Lösung aus einer ionischen Flüssigkeit und einem Metallvorläufer hergestellt, wobei die ionische Flüssigkeit sowohl als Kohlenstoffvorläufer als auch als Stickstoffquelle für die Metallnitride dient. Der Metallgehalt, das Metallverhältnis in ternären Nitriden und die Oberfläche sind über den Anteil des Metallvorläufers einstellbar. Schließlich werden beide Ansätze zur Salztemplatierung von den Kompositen kombiniert. Dadurch wird die Einschrittsynthese von Kompositen mit einstellbarer Oberfläche, Zusammensetzung, Partikelgröße und Morphologie ermöglicht. Diese Materialien wurden schließlich als Elektroden für Superkondensatoren getestet und der Einfluss verschiedener Parameter auf die Leistungsfähigkeit untersucht. Aufgrund verschiedener Kombinationsmöglichkeiten von ionischen Flüssigkeiten, Metallvorläufern und Salzen, stellen die hier präsentierten Ansätze eine vielversprechende Plattform für die nachhaltige Materialsynthese dar.
73

The study of crystallization and interfacial morphology in polymer/carbon nanotube composites

Minus, Marilyn Lillith 08 July 2008 (has links)
This study illustrates the ability of SWNT to nucleate and template polymer crystallization and orientation, and produce materials with improved properties and unique polymer morphologies. This research work focuses primarily on the physical interaction between single-wall carbon nanotubes (SWNT) and the flexible polymer system polyvinyl alcohol (PVA). Polymer crystallization in the near vicinity of SWNT (interphase) has been studied to understand the capability of SWNT in influence polymer morphology in bulk films and fibers. Fibrillar crystallization was achieved by shearing PVA/SWNT dispersions and resulted in the formation of oriented PVA/SWNT fibers or ribbons, while PVA solutions produce unoriented fibers. PVA single crystals were grown in PVA solutions as well as PVA/SWNT dispersions over a period of several months at room temperature (25 C). PVA single crystal growth in PVA/SWNT dispersions is templated by SWNT, and these crystals show the presence of new morphologies for PVA. PVA single crystals of differing morphology were also grown at elevated temperatures, and show morphology dependant electron beam irradiation resistance. Gel-spinning was used to produce PVA, and PVA/SWNT fibers where, PVA crystallization in the bulk fiber was observed. With 1 wt% SWNT loading in PVA, the fiber tensile strength increased from 1.6 GPa for the control PVA to 2.6 GPa for PVA/SWNT. Analysis of this data suggests stress of up to ~120 GPa on the SWNT. This is the highest reported stress on the SWNT to date and confirm excellent reinforcement and load transfer of SWNT in the PVA matrix. Raman spectroscopy data show high SWNT alignment in the fiber where the ratio is measured to be 106. High-resolution transmission electron microscopy (HR-TEM) is used to characterize polymer morphology near the polymer-SWNT interface for PVA/SWNT fibers. HR-TEM studies of Polymer/CNT composites show distinct morphological differences at the polymer-SWNT interface/interphase for semi-crystalline and amorphous polymer systems which may be related to polymer-SWNT interaction in the composite. Studies on polymer crystallization, carbon nanotube (CNT)/polymer composite, and polymer composite interfacial literature in summarized in Chapter 1. Fibrillar crystallization of PVA and PVA/SWNT is presented in Chapter 2. PVA single crystal grown at varying temperatures is discussed in Chapter 3, followed by single crystal growth studies in PVA/SWNT dispersions in Chapter 4. Chapter 5 summarizes the gel-spinning studies of PVA and PVA/SWNT fibers. Conclusions and recommendations for future work pertaining to this study are given in Chapter 6. Results of HR-TEM studies on other polymer/SWNT composites are given in Appendix A, Appendix B summarizes work on PE crystallization in the SWNT/DMF dispersions, and studies of PVA and PVA/SWNT gel films are summarized in Appendix C.
74

Simulação da propagação de ondas ultrassônicas longitudinais em materiais estruturais aeroespaciais / Simulating the propagation of longitudinal ultrasonic waves in aerospace structural materials

Leão, Rodrigo Junqueira 08 October 2012 (has links)
Orientador: Auteliano Antunes dos Santos Junior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T21:43:45Z (GMT). No. of bitstreams: 1 Leao_RodrigoJunqueira_M.pdf: 11585473 bytes, checksum: eb36aabbabd372414779881f910455a8 (MD5) Previous issue date: 2012 / Resumo: Materiais compósitos são cada vez mais utilizados na indústria aeroespacial, por apresentarem baixa relação entre massa específica e resistência mecânica. Para a realização de ensaios não destrutivos utilizando o ultrassom, faz-se necessário conhecer a velocidade com que o som se propaga através desses materiais. Nem sempre é possível desenvolver protótipos reais durante o desenvolvimento de um projeto, por limitações construtivas e de custo; modelos virtuais são, pois, necessários. O objetivo deste trabalho é desenvolver modelos virtuais para avaliar a propagação de ondas em compósitos e compará-los com resultados experimentais. Uma liga de alumínio é usada inicialmente, de forma a calibrar o modelo e configurar alguns parâmetros de simulação. O material composto analisado é um laminado unidirecional, fabricado a partir de 97 camadas de material pré-impregnado (AS4/8552) da Hexcel¿. Utiliza-se o método dos elementos finitos para simular a geração, propagação e recepção de ondas ultrassônicas no modelo. O foco do estudo são ondas longitudinais de volume, embora a geração de ondas longitudinais criticamente refratadas (Lcr) também seja demonstrada. A razão é que o estudo é parte de uma pesquisa sobre o desenvolvimento de técnicas ultrassônicas para a medição de tensões em compósitos, utilizando Acustoelasticidade. A fim de permitir a medição da velocidade da onda ultrassônica em diferentes orientações, foi fabricado um corpo de prova em formato de prisma de base poligonal de 24 lados. O modelo numérico desenvolvido considera o caso ideal, onde as lâminas são perfeitamente coladas umas nas outras e não há problemas como delaminação ou vazios. Um modelo simplificado de cada lâmina foi admitido, de modo a utilizar uma malha menos refinada nas simulações e reduzir o gasto computacional. A fração volumétrica de reforço e matriz foi mantida. Um pulso de 1 MHz foi inserido no modelo e as discretizações no tempo e no espaço foram escolhidas de forma coerente. Simulações para o caso de 0º e 90º foram feitas e um modelo para os outros ângulos de orientação foi proposto. Os resultados mostram-se satisfatórios e indicam que, no futuro, o modelo simplificado adotado poderá ser estendido, levando em conta não conformidades e uma distribuição mais heterogênea das fibras, permitindo o desenvolvimento de ferramentas de inspeção aperfeiçoadas / Abstract: The use of composite materials in the aerospace industry is increasing due to its low ratio between density and mechanical strength. To perform non-destructive testing using ultrasound, it is necessary to know the sound velocity in these materials. It is not always possible to manufacture physical prototypes during the development of a project because of time, construction limitation and cost; virtual models are therefore needed. The objective of this work is to develop virtual models to evaluate the wave propagation in composites and compare them with experimental results. Initially, an aluminum alloy is used in order to calibrate the model and configure some simulation parameters. The composite material analyzed is a unidirectional laminate, made from 97 layers of prepreg material (AS4/8552) from Hexcel¿. We use the finite element method to simulate the generation, propagation and reception of ultrasonic waves in the model. The focus of this study is the generation of longitudinal bulk waves, although the generation of Critically Refracted Longitudinal (Lcr) waves is also demonstrated. The reason is that the study is part of an ongoing research project on the development of ultrasonic techniques for measuring residual stress in composites, using acoustoelasticity. To enable the measurement of the ultrasonic wave velocity in different orientations, we manufactured a specimen in a prismatic shape (24-sided polygonal base). The numerical model consists of the ideal case, where the different materials are completely attached to each other and there are no problems such as delamination or voids. A simplified model of each layer was admitted, to use a less refined mesh in the simulations and reduce the computational cost. The volume fraction of reinforcement and matrix was maintained. A pulse of 1 MHz was inserted into the model and the discretization both in time and space was chosen consistently. Simulations for the case of 0° and 90° were made and a model for the other orientations was proposed. The results prove to be satisfactory and indicate that in the future, the simplified model adopted could be extended, taking into account nonconformities and a more heterogeneous distribution of the fibers, allowing the development of improved inspection tools / Mestrado / Mecanica dos Sólidos e Projeto Mecanico / Mestre em Engenharia Mecânica
75

ADVANCED PROCESSING OF NICKEL-TITANIUM-GRAPHITE BASED METAL MATRIX COMPOSITES

Patil, Amit k. 12 June 2019 (has links)
No description available.
76

MATERIAL RESPONSE TO FRETTING AND SLIDING WEAR PHENOMENA

Akshat Sharma (17963420) 14 February 2024 (has links)
<p dir="ltr">Fretting wear occurs when two contacting bodies under load are subjected to small amplitude oscillatory motion. Depending on the applied normal load, displacement amplitude, coefficient of friction and resulting shear force, two types of fretting wear regimes exist – (i) partial slip and (ii) gross slip. At displacement amplitudes higher than gross slip condition, sliding wear regime prevails. Fretting wear becomes dominant in machine components subject to vibrations such as bearings, dovetail joints, etc. whereas sliding wear is observed in brakes, piston-ring applications, etc. The work in this dissertation primarily focuses on characterizing the material response of various machine components subjected to fretting and sliding wear regimes.</p><p dir="ltr">At first, the friction and fretting wear behavior of inlet ring and spring clip components used in land-based gas turbines was investigated at elevated (<a href="" target="_blank">500°C</a>) temperature. In order to achieve this objective, a novel high-temperature fretting wear apparatus was designed and developed to simulate the conditions existing in a gas turbine. The test apparatus was used to investigate fretting wear of atmospheric plasma sprayed (APS) Cr<sub>3</sub>C<sub>2</sub>-NiCr (25% wt.), high-velocity oxy-fuel (HVOF) sprayed Cr<sub>3</sub>C<sub>2</sub>-NiCr (25% wt.), HVOF sprayed T-800 and APS sprayed PS400 coated inlet rings against HVOF-sprayed Cr<sub>3</sub>C<sub>2</sub>-NiCr (25% wt.) coated spring clip. The PS400 coated inlet rings demonstrated a significant reduction in friction and wear. A finite element (FE) framework was also developed to simulate fretting wear in HVOF-sprayed Cr<sub>3</sub>C<sub>2</sub>-NiCr composite cermet coating. The material microstructure was modelled using Voronoi tessellations with a log-normal distribution of grain size. Moreover, the individual material phases in the coating were randomly assigned to resemble the microstructure from an actual SEM micrograph. A damage mechanics based cohesive zone model with grain deletion algorithm was used to simulate debonding of the ceramic carbide phase from the matrix and resulting degradation from repeated fretting cycles. The specific wear rate obtained from the model for the existing material microstructure was benchmarked against experiments. Novel material microstructures were also modeled and demonstrated to show less scatter in wear rate.</p><p dir="ltr">Following, a three-dimensional (3D) continuum damage mechanics (CDM) FE model was developed to investigate the effects of fretting wear on rolling contact fatigue (RCF) of bearing steels. In order to determine the fretting scar geometry, a 3D arbitrary Lagrangian-Eulerian (ALE) adaptive mesh (AM) FE model was developed to simulate fretting wear between two elastic bodies for different initially pristine fretting pressures (0.5, 0.75 and 1 GPa) and friction coefficients (0.15, 0.175 and 0.25) resulting in stick zone to contact width ratios, c/a = 0.35, 0.55 and 0.75. The resulting wear profiles were subjected to various initially pristine RCF pressures (1, 2.2 and 3.4 GPa). The pressure profiles for RCF were determined by moving the contact over the fretted wear profiles in 21 steps. These pressure profiles were then used in the CDM-FE model to predict the RCF life of fretted surfaces. The results indicate that increased fretting pressure leads to more wear on the surface, thereby reducing RCF life. As the RCF pressure increases (P<sub>RCF</sub> ≥ 2.2 GPa), the effect of fretting on RCF life decreases for all fretting pressures and c/a values, indicating that life is primarily governed by the RCF pressure. The results from CDM-FE model were used to develop a life equation for evaluating the L<sub>10</sub> life of fretted M-50 bearing steel for the range of tested conditions.</p><p dir="ltr">Lastly, the sliding wear characteristics of pitch and poly-acrylonitrile based carbon-carbon (C/C) composites were investigated in air and nitrogen environment by designing and developing a disc brake test rig. It was found that the temperature of the disc, the surrounding environment, the supplied energy flux as well as the type of composite play a critical role in determining whether C/C composites operate in normal wear or dusting wear regime. Further analysis of wear mechanisms revealed interface and matrix cracking with fiber breakage from tests in air environment, whereas in nitrogen environment, particulate and layered debris played a prominent role.</p>
77

Thermoelectrical Properties of Covetics

Rana, S M Sarif January 2017 (has links)
No description available.
78

Composites à matrice carbone-oxyde et carbone-nitrure : thermodynamique de l'élaboration et son impact sur les propriétés physico-chimiques, thermiques et mécaniques des composites

Fontaine, Florian 13 January 2011 (has links)
Les composites carbone/carbone présentent de propriétés thermomécaniques à hautes températures qui les rendent particulièrement adaptés à l’ablation ou à la friction. Leur sensibilité à l’oxydation dès 400°C a conduit à envisager leur dopage en éléments réfractaires inoxydables ou à température d’oxydation élevée. Le procédé sol-gel a permis d’introduire environ 1 % volumique d’oxyde ou de nitrure de titane ou d’aluminium dans leur matrice. Les nitrures sont obtenus par nitruration carbothermique des films d’oxydes. Deux types de sols ont été utilisés : des sols « standard » et des sols enrichis en saccharose. Le saccharose est ajouté pour prévenir la consommation du pyrocarbone lors de la nitruration. Il a par ailleurs une influence sur l’avancement de la nitruration. Les composites chargés sont ensuite densifiés par voie gazeuse, ce qui induit des transformations de phases prévues par la thermodynamique : les films de nitrure de titane sont partiellement carburés (formation de carbonitrure), et les films d’oxyde de titane sont réduits (formation d’oxycarbure). Les dépôts à base d’aluminium sont plus stables et ne subissent aucune transformation. La diffusivité thermique des composites réalisés est faiblement impactée par les charges introduites, alors que les résistances en traction/compression sont sensiblement augmentées. Par ailleurs, une rigidification des composites est observée. Leur cinétique d’oxydation est ralentie. Les composites enrichis en alumine et nitrure d’aluminium présentent des vitesses de perte de masse divisées par 2 par rapport à la référence C/C. Toutes ces propriétés sont liées directement ou non à la composition des sols, et plus particulièrement à sa teneur en saccharose. Il a en effet été montré que les sols qui en contiennent ont tendance à gélifier en surface du composite, ce qui gêne la diffusion des gaz précurseurs au cœur du composite lors de la densification. La porosité finale s’en trouve modifiée. Cette dernière a une influence non négligeable sur le comportement en compression, la diffusivité thermique et la cinétique d’oxydation des composites élaborés. / Carbon/carbon composites exhibit excellent mechanical and thermal properties at high temperature that make them espe-cially suitable for ablation or friction pieces. Their sensitivity toward oxidation above 400°C has lead to the will of doping them with refractory ceramics that are nonoxidizable or with a high oxidation temperature. The sol-gel process allowed to introduce 1 % in volume of titanium or aluminum oxide or nitride in the matrix. Nitrides are obtained by carbothermal nitridation of the oxide films. Two types of sols were used: the “standard” ones and those with extra sucrose. Sucrose is added to prevent pyrocarbon consumption during the nitridation. Furthermore, it was shown that it has an impact on the nitridation rate. Charged composites are then densified by Chemical Vapor Infiltration, which induces phases transforma-tions that were predicted by thermodynamics: titanium nitride films are partially carburized (formation of titanium carbonitride) and titanium dioxide films are reduced (formation of titanium oxycarbide). Aluminum-based films are more stable and don’t undergo any transformation. Thermal diffusivity of the as-synthesized composites is not much modified by the addition of these ceramics while the tensile and compressive strength are slightly increased. By the way, composites are hardened. Their oxidation kinetics is slowed down. Aluminum-rich composites exhibit a weight loss divided by two compared to the C/C reference. All those properties are directly, or not, linked to the composition of the sols, in particular to their sucrose content. Indeed, it was shown that sucrose-containing sols rather jellify on the surface of the composite, thus preventing the diffusion of precursor gases to the heart of the pieces. The final porosity is then modified. The porosity has an important impact on the compressive strength, thermal diffusivity and oxidation kinetics of the synthesized composites.
79

Transition-metal-based composite and hybrid nanomaterials for catalytic applications

Zhang, Rui 12 June 2018 (has links)
In der Entwicklung von Technologien für die nachhaltige Erzeugung, Speicherung und Umwandlung von Energie werden Hochleistungskatalysatoren benötigt. Im Rahmen dieser Arbeit werden verschiedene Übergangsmetall-basierte Katalysatoren, namentlich TiO2/Kohlenstoff-Komposite, anorganisch-organische Hybridsysteme auf Basis von NiFe Phosphonaten sowie Ni Phosphide, synthetisiert, charakterisiert und hinsichtlich ihrer photo- und elektrokatalytischen Eigenschaften untersucht. Es wird gezeigt, dass die Grenzflächeneigenschaften der TiO2/C-Komposite signifikant durch die Gestaltung des Heizvorgangs während der Synthese beeinflusst werden. Insbesondere der Einsatz von Mikrowellenstrahlung vermag die Synthese von Kohlenstoff-basierten Materialien positiv zu beeinflussen. Schnelles Erwärmen führt zu stärkeren Wechselwirkungen zwischen Nanopartikeln und Kohlenstoff, einheitlicheren Beschichtungen und kleineren Partikeln mit schmaleren Partikelgrößenverteilungen, wodurch die photokatalytische Aktivität verbessert wird. Schichtartige, hybride NiFe-Phenylphosphonat-Materialien werden ausgehend in Benzylalkohol dargestellt und ihre Aktivität in der OER im basischen Milieu untersucht. Die Hybridpartikel werden in-situ in NiFe-Hydroxid Nanoschichten umgewandelt. Röntgenspektroskopische Untersuchungen deuten auf eine induzierte, teilweise verzerrte Koordinationsumgebung der Metallzentren im Katalysator hin. Die Kombination der synergistischen Effekte zwischen Ni und Fe mit den strukturellen Eigenschaften des Hybridmaterials ermöglicht einen effizienten Katalysator. Weiterhin werden Nickel-Phosphide durch die thermische Behandlung der Phenyl- oder Methylphosphonate des Nickels, welche Schichtstrukturen aufweisen, in H2(5%)/Ar-Atmosphäre synthetisiert. Ni12P5, Ni12P5-Ni2P und Ni2P Nanopartikel, die mit einer dünnen Schicht aus Kohlenstoffmaterial beschichtet sind, werden erhalten. Ni12P5-Ni2P und Ni2P Nanopartikel katalysieren die Wasserstoffentwicklungsreaktion (HER) im Sauren effektiv. / High-performance catalysts play a key role in the development of technologies for sustainable production, storage, and conversion of energy. In this thesis, transition-metal-based catalysts, including TiO2/carbon composites, hybrid organic-inorganic NiFe phosphonates, and Ni phosphides are synthesized, characterized, and investigated in photocatalytic or electrocatalytic reactions. TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (rGO), to produce composites with improved properties. TiO2 is more efficiently stabilized at the surface of rGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance. Layered hybrid NiFe-phenylphosphonate compounds are synthesized in benzyl alcohol, and their oxygen evolution reaction (OER) performance in alkaline medium is investigated. The hybrid particles transformed in situ into NiFe hydroxide nanosheets. X-ray absorption spectroscopy measurements suggest the metal sites in the active catalyst inherited partly the distorted coordination. The combination of the synergistic effect between Ni and Fe with the structural properties of the hybrid results in an efficient catalyst that generates a current density of 10 mA cm-2 at an overpotential of 240 mV. Moreover, nickel phosphides are synthesized through thermal treatment under H2(5%)/Ar of layered nickel phenyl- or methylphosphonates that act as single-source precursors. Ni12P5, Ni12P5-Ni2P and Ni2P nanoparticles coated with a thin shell of carbonaceous material are produced. Ni12P5-Ni2P and Ni2P NPs efficiently catalyze the hydrogen evolution reaction (HER) in acidic medium. Co2P and CoP NPs are also synthesized following this method.
80

Fonctionnalisation de matériaux composites à renfort carbone et matrice thermoplastique par adjonction de nanocharges : élaboration et étude du comportement / Functionalization of carbon fibers reinforced thermoplastic polymer by the use of nanofillers : fabrication and behavior study

Hamdi, Khalil 12 December 2017 (has links)
Pour étendre l'utilisation des composites dans des applications plus variées (applications intelligentes et multifonctionnelles), l'une des barrières est leur faible conductivité électrique et thermique. Dans le cas de composites renforcés par des fibres de carbone, la matrice organique est responsable des propriétés isolantes du composite résultant. L'une des solutions pour améliorer les conductivités des matériaux est l'utilisation des nanocharges conductrices. L'amélioration des propriétés électriques et thermiques des polymères nanochargés est une problématique récurrente dans la littérature. Cependant, étudier les propriétés des composites à fibre de carbone continue et nanochargés est moins abordée. Ce travail porte sur la fabrication et la caractérisation des composites nanochargés par du noir de carbone et des nanotubes de carbone. Tout d'abord, un intérêt particulier a été accordé à la phase délicate de la fabrication. Comme mentionné ci-dessus, la mise en œuvre des composites à renfort continu et matrice nanochargée implique des problèmes liés à l'agglomération et à la dispersion inhomogène des nanocharges dans le composite final. Pour résoudre ces problèmes, le choix de la matrice thermoplastique (Polyamide 6) était judicieux. En fait, la dispersion des nanocharges a été faite par extrusion bi-vis qui est connue comme l'une des voies les plus efficaces de séparation d'agglomérats. De plus, la méthode de fabrication à base de films de Polyamide 6, appelée film stacking, assure une partition homogène dès le début du processus. Des observations MEB ont été effectuées pour localiser les nanoparticules. Ceux-là ont montré que les particules pénétraient dans la zone des fibres. En effet, en atteignant le cœur des torons, les nano-charges ont créé un réseau de connectivité entre les fibres pour le passage de courant. Ceci explique l'amélioration constatée de la conductivité électrique des composites en présence de noir de carbone et des nanotubes de carbone. Ces essais ont été réalisés avec la méthode à 4 points. La conductivité électrique du composite à matrice « pure » est passée de 20S / cm à 80S / cm en ajoutant 8% en poids de noir de carbone et à 15S / cm en ajoutant 18% en poids de la même charge nanométrique. Pour les nanotubes de carbone, avec 2,5% en poids, la conductivité était d'environ 150S / cm. Pour les propriétés thermiques, des tests basés sur l'effet Joule ont été réalisés. L'augmentation de la température a été enregistrée en utilisant une caméra IR. Les résultats obtenus sont en accord avec ceux de la conductivité électrique, montrant une amélioration du comportement thermique en présence de nanocharges. Grâce à ces résultats, l'utilisation de ces composites comme outil de suivi d’endommagement était possible. Par ailleurs, la méthode de variation de la résistance électrique a été effectuée. Les matériaux nanochargés ont montré une meilleure sensibilité aux endommagements. Les résultats ont été comparés aux outils classiques de suivi d’endommagement. A la fin, plusieurs applications « intelligentes » ont été testées telles que : le composite à gradients de propriétés et des matériaux nanochargés cousus. / To extend the use of composites in more varied application (smart applications, multifunctional issues), one of the actual barrier is their poor electrical and thermal conductivities. In the case of carbon fiber reinforced composites, organic matrix are in charge of the insulating properties of the resulting composite. One of the solutions to enhance conductivities of materials is the use of conductive nanofillers. Improving the electrical and thermal properties of nanofilled polymers has been investigated in several studies. However, studiing the properties of continuous carbon fiber nano-filled composites is less approached. This work tends to fabricate and characterize carbon black and carbon nanotubes nano-filled composites. First of all, special interest was given to the delicate phase of manufacturing. As mentioned before, processing continuous fiber reinforced nanofilled polymers implies issues related to nanofillers agglomeration and inhomogeneous dispersion in the final composite. To resolve these problems, the choice of the thermoplastic (Polyamide6) matrix seemed preferable. In fact, the dispersion of nanofillers was made by twin screw extrusion which is known as one of the most effective agglomeration separation ways. Adding to this, the fabrication method based on Polyamide 6 shects called film stacking, ensure a homogeneous partition at the beginning of the process. SEM observations were performed to localize the nano-particles. It showed that particles penetrated on the fiber zone. In fact, by reaching the fiber zone, the nano-fillers created network connectivity between fibers which means an easy pathway for the current. It explains the noticed improvement of the electrical conductivity of the composites by adding carbon black and carbon nanotube. This test was performed with the 4 points electrical circuit. It shows that electrical conductivity of 'neat' matrix composite passed from 20S/cm to 80S/cm by adding 8wt% of carbon black and to 15S/cm by adding 18wt% of the same nano-filler. For carbon nanotubes, with '2.5wt% the conductivity was around 150S/cm. For the thermal properties, tests based on Joule's effect were performed. The rise of temperature was recorded using IR camera. Results obtained are in agreement with the electrical conductivity ones, showing enhancement of the thermal behavior in presence of nanofillers. Thanks to these results, the use of these composites as a damage-monitoring tool was possible. By the way, the electrical resistance change method was performed. Nanofilled materials showed better sensitivity to damage. Results were compared with classical damage monitoring tools. At the end, several 'smart' applications were tested such as graded functionalities composite and stitched nanofilled materials.

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