Toward a Better Understanding of the Gelation Mechanism of Methylcellulose via Systematic DSC Studies

A methylcellulose (MC) is one of the materials representatives performing unique thermal-responsive properties. While reaching a critical temperature upon heating MC undergoes a physical sol-gel transition and consequently becomes a gel. The MC has been studied for many years and researchers agree that the MC gelation is related to the lower critical solution temperature (LCST). Nevertheless, a precise description of the MC gelation mechanism remains under discussion. In this study, we explained the MC gelation mechanism through examination of a wide range of MC concentrations via differential scanning calorimetry (DSC). The results evidenced that MC gelation is a multistep thermoreversible process, manifested by three and two endotherms depending on MC concentration. The occurrence of the three endotherms for low MC concentrations during heating has not been reported in the literature before. We justify this phenomenon by manifestation of three various transitions. The first one manifests water–water interactions, i.e., spanning water network breakdown into small water clusters. It is clearly evidenced by additional normalization to the water content. The second effect corresponds to polymer–water interactions, i.e., breakdown of water cages surrounded methoxy groups of MC. The last one is related to the polymer–polymer interactions, i.e., fibril hydrophobic domain formation. Not only did these results clarify the MC crosslinking mechanism, but also in the future will help to assess MC relevance for various potential application fields.