Fibre Reinforced Polymer Composites are extensively used in aircraft structures because of its high specific stiffness, high specific strength and tailorability. Though Fibre Reinforced Polymers offer many advantages, they are not free from problems. The damage of different nature, e.g., service mechanical damages, fatigue damage or environmental damage can be observed during operating conditions. Among all the damages, manufacturing or service induced, delamination related damage is the most important failure mechanisms of aircraft-composite structures and can be detrimental for safety. Delamination growth under fatigue loading may take place due to local buckling, growth from free edges and notches such as holes, growth from ply-drops and impact damaged composites containing considerable delamination. Delamination growth can also occur due to interlaminar stresses, which can arise in complex structures due to unanticipated loading. The complex nature of composite failure, involving different failure modes and their interactions, makes it necessary to characterize/identify the relevant parameters for fatigue damage resistance, accumulation and life prediction. An effort has been made in this thesis to understand the fatigue behavior of carbon fibre reinforced epoxy laminates under aircraft wing service loading conditions. The study was made on laminates with different lay-up sequences (quasi-isotropic and fibre dominated) and different geometries (plain specimen, specimen with a hole and ply-drop specimen). The fatigue behaviour of the composite was analyzed by following methods: . Ultrasonic C-Scan was used to characterize the delamination growth. . Dynamic Mechanical Analysis (DMA) was done to study the interfacial degradation due to fatigue loading. In this analysis, the interfacial strength indicator and interfacial damping were calculated. The DMA also provides the storage modulus degradation under fatigue loading. . Scanning electron microscope examination was carried out to understand the fatigue damage mechanisms. . A semi-empirical phenomenological model was also used to estimate the residual fatigue life. This research work reveals that the Carbon Fibre Reinforced Polymer laminates are in the safe limit under service loading conditions, except the specimen with a hole. The specimen with a hole showed delaminations around the hole due to stress concentration and higher interlaminar stresses at the hole edges and this delamination is found to be associated with fibre breakage and fibre pullout. The quasi-isotropic laminate is found to show poorer fatigue behaviour when compared to fibre dominated laminate and ply-drop also shows poor performance due to high stress concentration in the ply-drop region.

L'objectif du projet de thèse est d'étudier et d'analyser le comportement mécanique à l'impact et en post impact de composites à fibres végétales. Le déroulement de cette thèse nécessite : L'élaboration et la caractérisation des matériaux de l'étude : Les matériaux de l'étude seront constitués de tissus à fibres végétales (lin et/ou chanvre) imprégnées de résine thermodurcissable (de type époxyde) ou thermoplastique (de type PP ou PLA). Ceux-ci seront fabriqués sous forme de plaque par la technique d'infusion sous vide ou la technique de la thermocompression, en fonction du type de résine. La caractérisation mécanique sera effectuée à partir d'essais mécaniques statiques et d'essais d'impact avec une tour de chute (à plusieurs niveaux d'énergie). Celle-ci sera d'abord menée sur des éprouvettes modèles (non impactées et non vieillis, sans et avec renfort fibreux) puis sur des éprouvettes dégradées (impactées à chaque niveau d'énergie et vieillis en humidité et température). La caractérisation de l'endommagement : Elle permettra, à partir des analyses d'images associées aux techniques de l'émission acoustique, de localiser et d'identifier les différents mécanismes d'endommagement intervenant dans ces matériaux au cours des diverses sollicitations choisies. Cette étude conduira à définir le degré de nocivité de ces endommagements tout en associant à la démarche l'influence des paramètres microstructuraux tels que la nature du renfort fibreux et des constituants (résine et fibres). L'identification de modèles de comportement : Il s'agit de proposer une méthode d'identification des paramètres matériaux de modèles de comportement tenant compte de l'endommagement au niveau de la microstructure du matériau (résine et torons de fibres). Cette étude conduira à la mise en œuvre d'une méthode de type recalage de modèles éléments finis en utilisant les bases de données expérimentales constituées notamment des mesures de champs cinématiques. L'objectif à terme est de disposer de modèles fiables et prédictifs pour le calcul de structures de ces matériaux dans l'industrie / The purpose of this PhD project is to study and analyze the mechanical behavior during the impact and post-impact of plant-fiber based composite materials. The conduct of this thesis requires: The manufacturing and characterization of the materials involved in the study : The materials are composed of plant-fiber fabrics (flax and/or hemp) impregnated with thermosetting resin (epoxy type) or thermoplastic resin (PP or PLA). These are manufactured using the vacuum infusion process or using thermocompression, depending on the resin. The materials are plate-shaped. The mechanical characterization will be performed using static mechanical testing and impact testing with a drop tower (over several energy levels). This will be first conducted on unmodified specimens (unimpacted and unaged, with and without fiber reinforcement) then on degraded specimens (impacted with a known energy and/or aged in humidity and temperature). The characterization of damage: It will, from the analysis of the images associated to the techniques of the acoustic emission, locate and identify the various damage mechanisms that intervene in these materials during different stresses. This study will lead to define the degree of harmfulness of such damage while associating to the approach the influence of microstructural parameters such as the nature of the fiber reinforcement and the components (resin and fibers). The identification of behavioral patterns: It consists in suggesting a method to identify the material parameters of behavioral patterns while taking into account the damage level of the material's microstructure (resin and fiber strands). This study will lead to the implementation of a finite element model updating-like method using experimental databases such as kinematic field measurements. The ultimate purpose is to have reliable and predictive models in order to calculate the structures of such materials in the industry

The poly(glycidyl methacrylate)-modified magnetite nanoparticles, Fe3O4-PGMA NPs, were investigated and applied in nondestructive flaw detection of polymeric materials in this research. The Fe3O4 endowed magnetic property to the materials for flaw detection while the PGMA promoted colloidal stability and prevented particle aggregation. The magnetite nanoparticles (Fe3O4 NPs) were successfully synthesized by coprecipitation and then surface-modified with PGMA to form PGMA-modified Fe3O4 NPs by both grafting-from and grafting-to approaches. For the grafting-from approach, the Fe3O4 NPs were surface-functionalized with α-bromo isobutyryl bromide (BIBB) to form BIB-modified Fe3O4 NPs (Fe3O4-BIB NPs) with covalent linkage. The resultant Fe3O4-BIB NPs were used as surface-initiators to grow PGMA by surface-initiated atom transfer radical polymerization (SI-ATRP). For the grafting-to approach, the Fe3O4 NP were surface-functionalized with (3-mercaptopropyl)triethoxysilane (MCTES) to form MCTES-modified Fe3O4 NPs (Fe3O4-MCTES NPs). The PGMA with Br-end group was pre-synthesized by ATRP and then was grafted to the surface of the Fe3O4-MCTES NPs by coupling reaction. Both bare and modified Fe3O4 NPs exhibited superparamagnetism and the existence of iron oxide in the form of Fe3O4 was confirmed. The particle size of individual Fe3O4 NPs was about 8 – 24 nm but they aggregated to form clusters. The PGMA-modified NPs formed stable dispersion in chloroform and had larger cluster sizes than the unmodified ones because of the PGMA polymer layer. However, the uniformity of the NP clusters could be improved with PGMA surface grafting. The PGMA surface layer of the grafting-from (Fe3O4-gf-PGMA) NPs was thin and dense while that of the grafting-to (Fe3O4-gt-PGMA) NPs was thick and loose. The hydrodynamic diameters (Zave) of Fe3O4-gf-PGMA NP clusters could be controlled between 176 to 643 nm, dependent on the PGMA contents and reaction conditions. During SI-ATRP, side reactions happened and caused NP aggregation as well as increase of size of NP clusters. However, the aggregation has been minimized through optimization of reaction conditions. Oppositely, Zave values of Fe3O4-gt-PGMA NPs had little variation of about 120 – 190 nm. And the PGMA content of the Fe3O4-gt-PGMA NPs was limited to 12.5% because of the spatial hindrance during grafting process. The saturation magnetization (Ms) of the unmodified Fe3O4 NPs was about 77 emu/g, while those of the grafting-from and grafting-to Fe3O4-PGMA NPs were 50 – 66 emu/g and 63 – 70 emu/g, respectively. For Fe3O4-PGMA NPs with similar Fe3O4 contents, the grafting-to NPs had slightly higher Ms than the grafting-from counterparts. In addition, the Ms of both kinds of the Fe3O4-PGMA NPs with higher Fe3O4 content (> 87%) were also higher than that of the fluidMAG-Amine, the commercially available amine-modified MNPs. Besides, both kinds of Fe3O4-PGMA NPs also had much higher Fe3O4 contents and Ms values than most of the reported PGMA-modified MNPs. The magnetic epoxy nanocomposites (MENCs) were prepared by blending the modified Fe3O4 NPs into bisphenol A diglycidyl ether (BADGE)-based epoxy system and the distributions of both kinds of the PGMA-modified NPs were much better than that of the oleic acid-modified Fe3O4 NPs. Similar to the NPs, the MENCs also exhibited superparamagnetism. By cross-section TEM observation, the grafting-to Fe3O4-PGMA NPs formed more homogeneous distributions with smaller cluster size than the grafting-from counterparts and gave higher Ms of the MENCs. Nondestructive flaw detection of surface and sub-surface defects could be successfully achieved by brightness contrast of images given through eddy current testing (ET) method, which is firstly reported. The mechanical properties of the materials were influenced very slightly when 2.5% or lower Fe3O4-gt-PGMA NPs were present while the presence of the Fe3O4-gf-PGMA NPs (1 – 2.5 %) gave mild improvement of the storage modulus and increase of the glass-rubber transition temperature(Tg) of the MENCs. Furthermore, the Fe3O4-PGMA NPs could be evenly coated onto the functionalized ultra-high molecular weight poly(ethylene) (UHMWPE) textiles. The Fe3O4-gt-PGMA NPs were coated on the textile in order to prepare NP-coated textile-reinforced composite. Preliminary result of ET measurement showed that the Fe3O4-gt-PGMA NPs coated on the textiles could visualize the structure of the textile hidden inside and their relative depth. Accordingly, the incorporation of MNPs to polymers opens a new pathway of damage-free structural health monitoring of polymeric materials.

The poly(glycidyl methacrylate)-modified magnetite nanoparticles, Fe3O4-PGMA NPs, were investigated and applied in nondestructive flaw detection of polymeric materials in this research. The Fe3O4 endowed magnetic property to the materials for flaw detection while the PGMA promoted colloidal stability and prevented particle aggregation. The magnetite nanoparticles (Fe3O4 NPs) were successfully synthesized by coprecipitation and then surface-modified with PGMA to form PGMA-modified Fe3O4 NPs by both grafting-from and grafting-to approaches. For the grafting-from approach, the Fe3O4 NPs were surface-functionalized with α-bromo isobutyryl bromide (BIBB) to form BIB-modified Fe3O4 NPs (Fe3O4-BIB NPs) with covalent linkage. The resultant Fe3O4-BIB NPs were used as surface-initiators to grow PGMA by surface-initiated atom transfer radical polymerization (SI-ATRP). For the grafting-to approach, the Fe3O4 NP were surface-functionalized with (3-mercaptopropyl)triethoxysilane (MCTES) to form MCTES-modified Fe3O4 NPs (Fe3O4-MCTES NPs). The PGMA with Br-end group was pre-synthesized by ATRP and then was grafted to the surface of the Fe3O4-MCTES NPs by coupling reaction. Both bare and modified Fe3O4 NPs exhibited superparamagnetism and the existence of iron oxide in the form of Fe3O4 was confirmed. The particle size of individual Fe3O4 NPs was about 8 – 24 nm but they aggregated to form clusters. The PGMA-modified NPs formed stable dispersion in chloroform and had larger cluster sizes than the unmodified ones because of the PGMA polymer layer. However, the uniformity of the NP clusters could be improved with PGMA surface grafting. The PGMA surface layer of the grafting-from (Fe3O4-gf-PGMA) NPs was thin and dense while that of the grafting-to (Fe3O4-gt-PGMA) NPs was thick and loose. The hydrodynamic diameters (Zave) of Fe3O4-gf-PGMA NP clusters could be controlled between 176 to 643 nm, dependent on the PGMA contents and reaction conditions. During SI-ATRP, side reactions happened and caused NP aggregation as well as increase of size of NP clusters. However, the aggregation has been minimized through optimization of reaction conditions. Oppositely, Zave values of Fe3O4-gt-PGMA NPs had little variation of about 120 – 190 nm. And the PGMA content of the Fe3O4-gt-PGMA NPs was limited to 12.5% because of the spatial hindrance during grafting process. The saturation magnetization (Ms) of the unmodified Fe3O4 NPs was about 77 emu/g, while those of the grafting-from and grafting-to Fe3O4-PGMA NPs were 50 – 66 emu/g and 63 – 70 emu/g, respectively. For Fe3O4-PGMA NPs with similar Fe3O4 contents, the grafting-to NPs had slightly higher Ms than the grafting-from counterparts. In addition, the Ms of both kinds of the Fe3O4-PGMA NPs with higher Fe3O4 content (> 87%) were also higher than that of the fluidMAG-Amine, the commercially available amine-modified MNPs. Besides, both kinds of Fe3O4-PGMA NPs also had much higher Fe3O4 contents and Ms values than most of the reported PGMA-modified MNPs. The magnetic epoxy nanocomposites (MENCs) were prepared by blending the modified Fe3O4 NPs into bisphenol A diglycidyl ether (BADGE)-based epoxy system and the distributions of both kinds of the PGMA-modified NPs were much better than that of the oleic acid-modified Fe3O4 NPs. Similar to the NPs, the MENCs also exhibited superparamagnetism. By cross-section TEM observation, the grafting-to Fe3O4-PGMA NPs formed more homogeneous distributions with smaller cluster size than the grafting-from counterparts and gave higher Ms of the MENCs. Nondestructive flaw detection of surface and sub-surface defects could be successfully achieved by brightness contrast of images given through eddy current testing (ET) method, which is firstly reported. The mechanical properties of the materials were influenced very slightly when 2.5% or lower Fe3O4-gt-PGMA NPs were present while the presence of the Fe3O4-gf-PGMA NPs (1 – 2.5 %) gave mild improvement of the storage modulus and increase of the glass-rubber transition temperature(Tg) of the MENCs. Furthermore, the Fe3O4-PGMA NPs could be evenly coated onto the functionalized ultra-high molecular weight poly(ethylene) (UHMWPE) textiles. The Fe3O4-gt-PGMA NPs were coated on the textile in order to prepare NP-coated textile-reinforced composite. Preliminary result of ET measurement showed that the Fe3O4-gt-PGMA NPs coated on the textiles could visualize the structure of the textile hidden inside and their relative depth. Accordingly, the incorporation of MNPs to polymers opens a new pathway of damage-free structural health monitoring of polymeric materials.:1. Introduction 2. Theoretical section 2.1. Magnetite Nanoparticles (MNPs) 2.2. Applications of MNPs 2.3. Atom transfer radical polymerization (ATRP) 2.4. Magnetic nanocomposites (MNCs) 2.5. Damage-free structural health monitoring (SHM) using MNPs 3. Objective of the work 4. Materials, methods and characterization 4.1. Materials 4.2. Methods 4.3. Formation of polymeric magnetic nanocomposites 4.4. Characterization 5. Results and discussions 5.1. Unmodified magnetite nanoparticles (Fe3O4 NPs) 5.2. Oleic acid-modified (Fe3O4–OA) NPs 5.3. PGMA-modified NPs by grafting-from approach (Fe3O4-gf-PGMA NPs) 5.4. PGMA-modified NP by grafting-to approach (Fe3O4-gt-PGMA NPs) 5.5. Comparison between grafting-from and grafting-to Fe3O4-PGMA NPs 5.6. Magnetic epoxy nanocomposites (MENCs) 5.7. Fiber-reinforced epoxy nanocomposites 6. Conclusions and outlook 7. Appendix 8. List of figures, schemes and tables 9. References Versicherung Erklaerung List of publications