Revealing the Filler-Matrix Interfacial Interactions: Real-Time Observation with Mechano-Responsive Spiropyran Microbeads.

Interfacial interactions between polymers and fillers play a crucial role in determining the performance of composite materials. In this study, mechano-responsive spiropyran (SP) beads, which exhibit fluorescence changes under stress, serve as force probes to evaluate force transfer efficiency across two types of interfaces: noncovalent and covalent. These interfaces are engineered by respectively employing physical blending and grafting polymerization to integrate hydroxyl SP beads with a polyurethane (PU) matrix. A custom-built in situ opto-mechanical setup quantitatively assesses force transfer by monitoring changes in fluorescence intensity and peak wavelength during specimen stretching. The analysis reveals that the covalent interface significantly outperforms the noncovalent interface, demonstrating a 100% improvement in force magnitude and transfer rate from the PU matrix to the SP beads. Direct observation of SP beads within the PU matrix during tension unveils that enhanced force transfer efficiency is closely linked to changes in the SP beads' aspect ratio. Fluorescence changes in SP beads are solely a function of aspect ratio, making them effective independent force probes.

Smart Materials with Dual Functionality: Repeatable Damage-Detection and Self-Healing.

Polymer materials are extensively used because of their excellent performance; however, when used for a long time, they break and eventually lose their original properties. Thus, smart polymer materials that can repeatedly detect and repair damage must be urgently developed to increase their durability and lifespan. In this study, a smart material with dual functionality (damage-detection and self-healing) is developed via a facile method of incorporating spiropyran (SP) beads, which exhibit changes in color and fluorescence when damaged, into a Diels-Alder (DA)-based self-healing matrix. When polyurethane (PU) is added to the DA-based matrix, the dual functionality exhibits a strong dependence on the proportion of PU. Because the PU ratio affects two opposing factors (damaged area and load-bearing capacity), the damage-detecting ability exhibits the best performance at 40 wt % PU, where both factors are optimized. A high healing efficiency of 96% is achieved via a dynamic DA reaction. In particular, the repeatability of the dual-functionality is successfully attained through the reversibility of the SP beads and DA networks, where the detection and healing efficiencies are reduced by 15 and 23%, respectively, after 10 cycles. Furthermore, the reprocessed fractured specimens exhibit excellent recyclability.

Revealing the Dependence of Molecular-Level Force Transfer and Distribution on Polymer Cross-Link Density via Mechanophores.

The correlation between polymer architecture and molecular-level forces has long been a challenging research subject. Herein, spiropyran, a mechanophore that exhibits fluorescence change under force, was incorporated as a cross-linker between PMMA backbone segments. Using an in situ opto-mechanical setup to probe the molecular-level forces, the mechano-response of SP-linked PMMA as a function of the cross-link density was monitored during deformation. The dependence of the molecular-level force on cross-link density was quantitatively examined and revealed. First, a higher cross-link density shifted the fluorescence onset, that is, the onset of the spiropyran-to-merocyanine transition, to lower strains, eventually shifting the onset long before yield, without requiring sufficient chain mobility, owing to the higher efficiency of the force transfer. Under the same energy, the increase in cross-link density allowed for faster force transfer, but only to a certain level. Finally, the overall amount of spiropyran-to-merocyanine conversion linearly decreased with increasing cross-link density.