High-Temperature-Aging Induced Sequential Recovery of Shape Memory Nitrile Butadiene Rubber Composites.

Abstract

The sacrificial bonds in natural materials have inspired the preparation of shape memory polymer (SMP), which can be prepared through the construction of dual cross-linking networks in a polymer matrix. With the rise of 4D printing technology, fine control over the shape recovery of SMPs, especially control over the recovery time, is urgently needed. In this study, the high-temperature aging method is adopted to tune the shape recovery time of dual cross-linked SMPs. Shape memory acrylonitrile butadiene rubber composite (i.e., NBR-C) is prepared by introducing Zn2+-C≡N coordination bonding and sulfur covalent cross-linking networks into the rubber matrix and then thermal aging at 180 °C for various time frames. Aging increases the covalent cross-linking density, ruptures rubber chains, and generates imine structures. Moreover, the composition of the coordination bonding network becomes diversified because of the formation of coordination bonds between imines and Zn2+ ions. The mechanical "tough-brittle" transition of aged NBR-C is observed, and its glassy temperature increases with aging time, which in turn changes the shape recovery time at the same recovery temperature. On the basis of these findings, the special shape memory rubber components with sequential recovery are fabricated by partially aging the NBR-C strings. This methodology provides novel solutions for the preparation of sequential SMP products without programming heating design or using redundant chemical materials. We believe that this work will be able to help promote comprehensive research of SMPs and widen applications of SMPs in the industry.