Using Nanosphere Embedding to Probe the Surface and Bulk Relaxation in Vitrimers.

Abstract

The relaxation behavior of vitrimers that is dominated by chemical exchange reactions plays a critical role in vitrimer processing and applications such as self-healing, welding, and others involving the dynamic nature of the vitrimers. Here, we use atomic force microscopy to image embedding of gold nanospheres into epoxy-based vitrimers to assess the surface and bulk relaxation in this material. The results show that even at temperatures well below the bulk topology freezing transition temperature, the nanospheres embed into the vitrimers. The activation energy for the relaxation at the surface and in bulk were estimated in the single measurement, and the former is found to be much lower than the latter. The increase in the surface relaxation is attributed to a combination of an acceleration effect on relaxation by network defects and a decrease in the number of intermolecular exchanges at the surface.