Hydrogen-bond-dominated mechanical stretchability in PVA films: from phenomenological to numerical insights

Hydrogen bonds (H-bonds) in poly(vinyl alcohol) (PVA) play a crucial role in macroscopic mechanical properties, particularly for stretchability. However, there is still some ambiguity about the quantitative dependence of H-bond interactions on the mechanical performance, mainly attributed to the difficulty in the discrimination of various H-bond types. Herein, small molecular chemicals as plasticizers were incorporated into the PVA matrix to tailor the H-bonding interactions. By altering the PVA molecular weight, plasticizer type and loading, both the stretchability and H-bond content were regulated on a large scale. By a combination of DMA, IR spectroscopy, MD simulation and solid-state C-13-NMR, every sort of H-bond in PVA was assigned, and their relative fractions were ascertained quantitatively. After correlating the elongation ratio with the relative fraction of the different types of H-bonding interaction, it was found that all the pairs of elongation vs. intermolecular H-bond content derived from different series of PVA/plasticizer films could be plotted into a master curve and exhibited good linearity, indicating that intermolecular H-bonds dominate the mechanical stretchability in PVA films. Our efforts contribute towards an in-depth understanding of performance optimization induced by H-bond manipulation from empirical, phenomenological aspects to intrinsic, numerical insights.

Automated summary

This study successfully regulated the stretchability and hydrogen bond content of PVA films by incorporating small molecular chemicals as plasticizers into the PVA matrix. Through various analytical techniques, it was demonstrated that intermolecular hydrogen bonds dominate the mechanical stretchability of PVA films.