Molecular modeling of amorphous and crosslinked cellulose

Structure-property relationships in cellulose crosslinked with both conventional and elastomeric crosslinking agents were successfully calculated using molecular modeling. The observed yielding for these amorphous cellulose models, which occurred at approximately 8% strain according to the calculated stress-strain relationship, is due to the disruption of hydrogen bonds, the secondary crosslinks, between cellulose chain segments. Crosslinks hold cellulose chain segments together and block chain slippage to give cellulose fibers a higher initial modulus and better elastic response. However, these crosslinks restrict chain movement so that stress is concentrated in regions of the structure and cavities are formed and developed in these regions of the models, which correlate to final fiber failure.; The flexibility and response to applied external force for some potential crosslink structures were examined by molecular modeling. These molecules, which have small energy differences between conformational states, are highly coiled and have small mean end-to-end distances (accounting for 40% to 50% of the length of their fully extended chains). The presence of oxygen atoms in the backbone along with asymmetric non-polar side groups, such as methyl groups, can greatly reduce the energy difference and the energy barrier between conformational states and can thus make chains highly coiled and easy to be extended. Decane crosslinks introduced more freedom to cellulose chain segments but didn't improve the deformation recovery in cellulose models. Conformational transitions were observed in decane crosslinks during deformation. Cellulose models crosslinked with poly(propylene oxide) pentamers or with the N-methyl substituted peptide pentamers show good deformation recovery without affecting the breaking strain. Both crosslinks didn't significantly change the initial modulus and the yielding behavior of cellulose. No conformation transitions were observed in these crosslinks when crosslinked cellulose models were strained to 15% strain. These highly coiled, spring-like molecules are candidates for elastomeric crosslinking agents for cellulose materials.; Improvement in deformation recovery of cellulose models by elastomeric crosslinks is achieved by breaking newly formed hydrogen bonds and restoring the original hydrogen bonds. Elastomeric crosslinks can improve the deformation recovery of cellulose models without affecting the mechanical strength of cellulose.