Network formation in graphene oxide composites with surface grafted PNIPAM chains in aqueous solution characterized by rheological experiments

Poly N-isopropyl acrylamide (PNI) radically polymerized in aqueous solution in the presence of graphene oxide (GO) can significantly change the properties of the resulting solution from a regular polymer solution to a soft solid with a GO content of only 0.176 wt% (3 wt% with respect to PNI). However, these properties require the presence of both grafting and supramolecular interactions between polymer chains and hydrophilic groups on GO (-OH, -COOH), proven by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction and spectroscopy (XRD) and Raman spectra. While very low GO-contents (below 0.05 wt%) only lead to a labile structure, which can be disassembled by shear, higher contents yield composites with solid-like characteristics. This is clearly evident from the rheological behaviour, which changes significantly at a GO content around 0.15 wt%. Intensive shearing destroys the weak network, which cannot reform quickly at lower GO-concentrations, while at intermediate concentrations, restructuring is fast. GO-contents of 0.176 wt% lead to a material behaviour, which almost perfectly recovers from small deformations (creep and creep recovery compliance almost match) but larger deformations lead to permanent damage to the sample.