Advanced polymer nanocomposites with tailored morphologies for high voltage insulating systems

摘要

This thesis reports different approaches to prepare a new generation of nanostructured insulating materials featuring controlled nanoparticles dispersion, using block copolymers and polymer blends as template matrices. Two types of nanoparticles, both organically modified, were used: zinc oxide (ZnO) and Montmorillonite clay. In addition, polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) triblock copolymer, composed of two polystyrene (PS) endblocks in the form of well-ordered nanodomains and one poly(ethylene-co-butylene) (PEB) elastomer middle block, was selected as a template matrix.ududSEBS/clay and SEBS/ZnO nanocomposites featuring different configurations of PS domains and clay platelets, namely: isotropic, partially oriented and oriented morphologies were achieved by varying the processing techniques. Besides, the spatial distribution of clay platelets and ZnO nanospheres and their affinities to either PS block or PEB block were tuned by the presence or not of maleic anhydride (MA) graft attached to PEB block. In particular, the dispersion of both types of nanoparticles was considerably improved in the presence of MA. Dielectric, rheological, thermal and mechanical properties of these nanocomposites were characterized in correlation with their morphologies.ududIn SEBS/clay nanocomposites, it was found that the incorporation of clay induced slower dynamics of PEB chains located in the interfacial region. A new interfacial glass transition (Tgi), higher than the glass transition (Tg) of bulk PEB, was attributed to these interfacial chains. Furthermore, the orientation and location of clay affected the interfacial dynamics: the highest Tgi temperatures were related to samples with lower alignment degree and preferential location of clay in PEB phase. Functional properties were also affected by the orientation. To be more specific, SEBS/clay nanocomposites with totally aligned clay platelets and PS domains were simultaneously the most efficient in improving the breakdown strength up to 45% and the less efficient in improving the mechanical strength. However, nanocomposites with partially oriented morphologies provided the best combination of dielectric breakdown strength and mechanical strength.ududIn SEBS/ZnO nanocomposites, the improved dispersion and affinity to PEB block, achieved in the presence of MA, induced the formation of networks between ZnO nanoparticles and SEBS chains. This behavior was accompanied by an increase of thermal conductivity and excellent improvement of the resistance to surface erosion: eroded volume reduced by 90% at only 5wt% ZnO. In the last part of the project, selected SEBS/ZnO nanocomposites were mixed with polyethylene (PE) to prepare blend nanocomposites as new candidates for HV insulation. Although the overall dielectric performance of unfilled PE/SEBS blend was reduced compared to neat PE, PE/SEBS/ZnO blend nanocomposites featured higher resistance to surface erosion and mechanical flexibility compared to conventional PE/ZnO nanocomposites. This improvement was correlated with the improved dispersion of ZnO nanoparticles in PE/SEBS/ZnO compared to PE/ZnO nanocomposites and their selective localization in SEBS phase and potentially at the interfaces between PE and SEBS.