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

<p> Over the past decade, the development of surface-initiated living polymerization methods has brought a breakthrough to surface modification owing to their control ability. Surface-initiated atom transfer radical polymerization (si-ATRP), as the most popular one, has been widely employed to give novel polymer structures and functionalities to various surfaces for the purposes of tailoring surface properties, introducing new functions, or preparing so-called "smart surfaces", which can respond to external stimuli such as solvent type, pH, temperature, electric and magnetic fields etc. In this thesis, the mechanistic study of the si-ATRP was first carried out through modeling to gain good understanding of si-ATRP. Si-ATRP was then employed to prepare different types of polymer brushes to produce "smart surfaces". </p> <p> The kinetic model was developed using the method of moment. Combined with experimental data, a quantitative analysis was carried out for the si-ATRP mechanism. All information of grafted polymer chains, including active chain concentration, radical concentration, chain length, polydispersity, was illustrated. A new radical termination mechanism, termed as migration-termination, was proposed for si-ATRP. </p> <p> Si-ATRP was then employed to graft poly(oligo(ethylene glycol) methacrylate) (POEGMA) block poly(methyl methacrylate) (PMMA) brushes on silicon wafer surfaces. Simple solvent treatment gave nanoscale patterns via the phase segregation of POEGMA and PMMA segments. Various patterns including spherical aggregates, wormlike aggregates, stripe patterns, perforated layers and complete overlayers, were obtained by adjusting the upper block layer thickness. Furthermore, these nanopatterns had a unique stimuli-responsive property, i.e., switching between different morphologies reversibly after being treated with selective solvents. </p> <p> POEGMA-block-poly(2-(methacryloyloxy)ethyl trimethylammonium chloride) (PMETAC) brushes, having two hydrophilic segments, were synthesized by si-ATRP method. A variety of nanopatterns and their stimuli-responsive ability were observed. The adsorption behaviors of fibrinogen on these patterns were thoroughly studied by ellipsometry, water contact angel measurement, AFM and radio labelling method. </p> <p> A novel thermo-responsive copolymer, poly(2-(2-methoxyethoxy)ethyl methacrylate -co-oligo(ethylene glycol) methacrylate) (P(ME02MA-co-OEGMA)), was also grafted onto silicon wafers. Its thermo-responsive behavior and chain conformation in aqueous solution were studied by neutron reflectometry (NR). Both extended and collapsed brushes exhibited good protein adsorption resistance. </p> / Thesis / Doctor of Philosophy (PhD)

De nouveaux glycopolymères greffés aux paramètres macromoléculaires contrôlés [dextrane-g-poly(acrylate de diéthylène glycol cholestéryle), Dex-g-PADEGChol] ont été préparés en quatre étapes via la stratégie de synthèse « grafting from». L'originalité de ces glycopolymères réside dans la combinaison, et pour la première fois, d'une dorsale polysaccharide hydrophile biocompatible/ biodégradable et de greffons polymères hydrophobes à caractère mésogène. L'ATRP a été utilisée pour contrôler la croissance des greffons PADEGChol en milieu homogène à partir d'un macroamorceur dérivé de dextrane (DexAcBr). Les conditions de polymérisation avaient été préalablement ajustées en étudiant l'homopolymérisation du monomère ADEGChol en présence d'un amorceur modèle et de plusieurs systèmes catalytiques CuIBr/(PMDETA ou OPMI) dans différents solvants (THF ou toluène). Le caractère amphiphile de ces glycopolymères a été évalué et leurs propriétés mésomorphes ont été étudiées par calorimétrie différentielle à balayage, microscopie optique à lumière polarisante et par diffraction des rayons X. Des études préliminaires par microscope électronique à transmission et diffusion dynamique de la lumière polarisée ont démontré que ces glycopolymères adoptent une morphologie vésiculaire appelée « polymersome » en phase aqueuse, lorsque le DMSO est utilisé comme co-solvant. Ces nano-objets pourront être testés ultérieurement pour la formulation d'un nouveau type de vecteurs de principes actifs / New graft glycopolymers with well-defined parameters [dextran-g-poly(diethylene glycol cholesteryl ether acrylate) (Dex-g-PADEGChol)] have been prepared in four steps using the "grafting from" strategy. Challenge of this work arises from the combination for the first time of a hydrophilic, biocompatible/biodegradable polysaccharide backbone with mesogen hydrophobic polymeric grafts. Controlled growth of the grafts (PADEGChol) was obtained using ATRP initiated in homogeneous medium from a dextran derivative (DexAcBr). In order to find the best polymerization conditions, homopolymerization of ADEGChol monomer was investigated using an initiator model and various catalytic systems CuIBr/(PMDETA or OPMI) in two solvents (Toluene and THF). The amphiphilic properties of such glycopolymers were evaluated and their mesomorphic properties have been studied by thermal polarizing optical microscopy, differential scanning calorimetry and X-ray scattering. Using transmission electron microscopy and dynamic light scattering, vesicular morphology called "polymersome" was observed in aqueous medium when DMSO was used as co-solvent. These polymersomes could be tested as new drug delivery systems