Mechanisms of oxygen- and argon-RF-plasma-induced surface chemistry of cellulose

Pure cellulose samples were Ar- and O2-RF-plasma treated under various external plasma parameter conditions. Plasma induced macromolecular chain and pyranosidic ring cleavage mechanisms are discussed based on survey and high resolution ESCA and ATR-FTIR analysis of cellulose, discharge-exposed cellulose, and discharge-exposed and TFAA and PFPH-derivatized cellulose samples. Analyses have also been made of bothin situ andex situ post plasma oxidation reactions. The new plasma created functionalities were identified and their relative ratios were related to plasma parameters. It was found that Ar plasma treatments initiate reactions mainly associated with the cleavage of C1–C2 linkages leading to the formation of C=O and O-CO-O groups, while O2-plasma treatments are associated with more intense pyranosidic ring (C-O-C bonds) splitting mechanisms. As a result of our detailed investigation of the high resolution C1s spectra of cellulose and carbohydrates we have reassigned the nonequivalent carbon bond affiliation (C-OH, C-O-C, and C-C) at 285–287 eV.