Molecular mechanisms for the adhesion of chitin and chitosan to montmorillonite clay
(English)Manuscript (preprint) (Other academic)
Molecular dynamics simulations have been performed to investigate molecular adhesion of chitin and chitosan oligomers to montmorillonite (Mnt) clay at different degrees of acetylation (DA, 0%, 20%, 40%, 60%, 80% and 100%) and different degree of protonation (DPr, 0%, 50%, 100% mimicking pH > 6.5, pH = 6.5, pH < 4, respectively) under fully hydrated conditions. Although the Mnt surface is negatively charged and a variation in DA also implies going from a positively charged oligomer at DA = 0% to a neutral oligomer at DA = 100%, the simulations show unexpectedly variation of the total molecular adhesion as a function of DA. From our analysis we propose that this quantitatively similar adhesion arise from two different mechanisms. At low DA, the oligomer is rich in positively charged amino groups interacting strongly with the negatively charged surface by direct electrostatic interaction. On the other hand, at high DA, electrically neutral acetyl groups are strongly correlated with the Na+ counter ions, which are in all cases stuck at the surface and the counter ions seem to act as ‘glue’ between the acetyl groups and the Mnt. However, when protonation was decreased, adhesion was significantly lowered. The reason is conclued by differences in charge distributions of the respective functional groups. A further investigation on the intramolecular hydrogen bonds formed in CHT or CHS shows that the adsorbed conformation of the polymer is also highly affected by DA. This work provides fundamental insights into adhesion mechanisms and is, of potential importance for the development of polymer-clay based composite materials.
molecular modelling, bio-nanocomposite, intramolecular hydrogen bonds, interfacial adhesion
Theoretical Chemistry Materials Chemistry Physical Chemistry
Research subject Fibre and Polymer Science; Chemistry; Materials Science and Engineering
IdentifiersURN: urn:nbn:se:kth:diva-166292OAI: oai:DiVA.org:kth-166292DiVA: diva2:810444
QS 20152015-05-072015-05-072015-05-20Bibliographically approved