Real-Time Quantification of Polyethylene Crystallinity via In Situ Mid- and Near-Infrared Correlation Spectroscopy: Melting and Dissolution

Elucidating the crystalline-amorphous interface during decrystallization processes in semi-crystalline polyethylene (PE) is crucial for the advancement of polymer theory and plastic-to-plastic recycling technologies. In this study, we carried out an in-depth investigation of PE thin films undergoing melting or dissolution using a temperature-controlled liquid flow-cell experimental setup which provided in situ mid-infrared (MIR, 4000–700 cm⁻¹) and near-infrared (NIR, 6000–4000 cm⁻¹) spectra in real time. The spectroscopic results yielded molecular-level information regarding PE decrystallization and chain disentanglement via fundamental vibrations, combination bands, and overtones which were correlated using hetero-spectral two-dimensional correlation spectroscopy (2D-COS). A quantitative procedure for the calculation of PE degree of crystallinity was developed to track transformations of crystalline domains during melting and dissolution. This semi-empirical model achieved a strong linear correlation of at least +0.93 in four spectral regions: 750–700 cm⁻¹, 1500–1400 cm⁻¹, 3000–2800 cm⁻¹, and 4400–4200 cm⁻¹. This analysis revealed important spectral trends about the interfacial solvation environment during these processes. Lastly, the time evolution of the unraveling, terminal methyl (.CH₃) groups of PE cilia was examined in relation to the decrystallization mechanism of PE. The insights obtained from this study advance the fundamental understanding necessary for developing new depolymerization and dissolution-precipitation recycling strategies.