FTIR in situ transmission studies on the kinetics of paper degradation via hydrolytic and oxidative reaction paths

This study deals with the quantitative and qualitative interpretation of transmission FTIR spectra of aged model paper samples to prepare the basis for a kinetic model of cellulose degradation involving mixed hydrolytic and oxidative mechanism. The ageing experiments were performed in situ under various conditions (pure water vapour, dried air, 100, 150 °C) to discriminate between hydrolytic and oxidative paths. Our focus was on the spectra between 1500–1900 cm^-1, where the products of paper ageing appear in the form of various carbonyl groups. A procedure of spectra standardization was used to interpret the bands area in terms of the conversion of carbon atoms in cellulose. From the time evolution of the bands the overall kinetic curves were generated. The positions of the carbonyl bands were verified by independent experiments and theoretical calculations (DFT method). A simple model involving a hydrolytic reaction route and first order kinetics was positively tested on the available experimental basis. PACS 81.05.-t; 82.20.Wt; 87.15.Rn