Cellulose consolidated with polyethylene glycol: The nanoscale mechanisms revealed by hybrid Monte Carlo/molecular dynamics modeling.

Polyethylene glycol (PEG) consolidation treatment is a widely used conservation strategy for wooden culture relics. However, the consolidation mechanism of PEG is still open to interpretation. PEG-cellulose, the representative component of wood cell wall, interactions are governed by various coupled multi-scale mechanisms which require nano-scale investigation. In this study, a hybrid molecular dynamics and grand canonical Monte Carlo (MD/GCMC) simulation combined with rule of mixture (RoM) analyses are employed to reveal the underlying mechanisms of PEG-induced consolidation. We found that PEG200 reduces moisture adsorption and swelling at museological conditions, confirming its consolidation effect. At high PEG content, a crossover behavior is identified at humid conditions (RH > 80) where excessive sorption and swelling are observed surpassing the untreated sample. The molecular modeling results are found to be consistent with experimental observations. Furthermore, the structural and mechanical properties of the hydrated samples are assessed by examining the porosity distribution, mechanical properties, and hydrogen bonding network. Results indicate mechanical softening induced by PEG treatment. A modified mixture model is proposed based on molecular modeling results that incorporate sorption and swelling coupling, porosity filling and mechanical softening behaviors. Two key mechanisms are identified explaining the consolidation effect of PEG: first, the PEG fills the porosities of amorphous structure thus diminishing sorption sites; second, the polymer structure prohibits PEG from further swelling thus constraining water sorption. The model and theoretical framework can serve as a guide for the design of novel consolidant materials by identifying the key molecular features of an ideal consolidant.