Sophie Peeterbroeck

Functionalization of carbon nanotubes by atomic nitrogen formed in a microwave plasma Ar + N2 and subsequent poly(ε-caprolactone) grafting

Multi-walled carbon nanotubes (MWNTs) are placed under atomic nitrogen flow formed through an Ar + N2 microwave plasma in order to functionalize covalently their side walls with nitrogen-containing groups. The MWNT surface analyzed by X-ray photoelectron spectroscopy shows the presence of amides, oximes and mainly amine and nitrile functions grafted in this way. In order to highlight the actual location of the amine functions grafted on MWNTs, they were considered as initiation species in ring-opening polymerization of e-caprolactone using triethylaluminium as activator. The so-generated poly(e-caprolactone) chains remain grafted on the MWNTs via amide bonds and form polyester islets along the nanotubes surface. TEM images of these MWNT surfaces grafted with poly(e-caprolactone) show a good amino-sidewall distribution. This work demonstrates the side-wall amino-functionalization of carbon nanotubes readily achieved by microwave plasma with the possibility to reach within a short time period very high contents in nitrogen-based functions (∼10 at.%).

Study of interlayer spacing collapse during polymer/clay nanocomposite melt intercalation.

The influence of the chemical structure of alkylammonium organo-modifying montmorillonite clays on the ability to form nanocomposites by melt blending, depending on the processing temperature and the organoclay thermal treatment, has been investigated. On one side chlorinated polyethylene/Cloisite 30B (nano)composite has been prepared by melt intercalation at 175 degrees C and its wide angle X-ray diffraction pattern revealed that the peak characteristic of the interlayer spacing of the organoclay was shifted to lower d-spacing, indicating a collapse of the organoclay structure. On the other side, (nano)composites based on ethylene-vinyl acetate copolymer/Cloisite 30B have been prepared by melt intercalation at 140 degrees C. At this temperature, exfoliation was observed with the as-received organoclay while the same organo-modified clay, simply dried at 180 degrees C for 2 hours, induced again the formation of a composite with a collapsed structure. The effect of the Cloisite 30B thermal treatment on the morphology and mechanical properties of ethylene-vinyl acetate-based (nano)composites was investigated using wide angle X-ray diffraction and tensile tests. In order to shed some light on the origin of this clay interlayer collapse, organoclay modified with various ammonium cations bearing long alkyl chains with different amounts of unsaturations were studied using wide angle X-ray diffraction and X-ray photoelectron spectroscopy before and after thermal treatment at 180 degrees C for 2 hours. Isothermal thermogravimetric analysis of all organoclays was also investigated. The layers collapse effect is discussed depending upon the level of unsatured hydrocarbon present in the organic surfactant.