Optimizing supramolecular architecture and performance of starch/polyacrylamide films via precise temperature‐mediated hydrogen bonding

Abstract Film‐forming temperature is a critical parameter for tuning the properties of starch‐based materials. In this study, the influence of film‐forming temperature (30–110 °C) on the structure and properties of polyacrylamide (PAM) modified starch films was systematically investigated. The results demonstrated that at 70 °C an optimal balance between molecular‐chain mobility and water evaporation rate was achieved, facilitating the formation of the most stable hydrogen‐bonding network between starch and PAM, with an associated –OH group content of 33.4%. This molecular‐level optimization promoted well‐ordered assembly of the supramolecular architecture, resulting in high crystallinity (16.98%). Consequently, the synergistic effects of this multilevel architecture endowed the S/PAM‐70 film with excellent thermal stability, moisture‐barrier properties and humidity resistance. In contrast, excessively low (≤50 °C) or high (≥90 °C) temperatures caused incomplete hydrogen‐bond formation or ‘flash‐evaporation’ (induced freezing of molecular chains), respectively, leading to increased structural defects and a marked decline in performance. © 2026 Society of Chemical Industry.