Advancing elastomer performance with dynamic bond networks in polymer-grafted single-chain nanoparticles: a molecular dynamics exploration.

This research introduces a method to enhance the mechanical properties of elastomers by grafting polymer chains onto single-chain flexible nanoparticles (SCNPs) and incorporating dynamic functional groups. Drawing on developments in grafting polymers onto hard nanoparticle fillers, this method employs the distinct flexibility of SCNPs to diminish heterogeneity and enhance core size control. We use molecular dynamics (MD) simulations for a mesoscale analysis of structural properties, particularly the effects of dynamic functional group quantities and their distribution. The findings demonstrate that increased quantities of functional groups are correlated with enhanced mechanical strength and toughness, showing improved stress-strain responses and energy dissipation capabilities. Moreover, the uniformity in the distribution of these functional groups is crucial, promoting a more cohesive and stable dynamic bonding network. The insights gained from MD simulations not only advance our understanding of the microstructural control necessary for optimizing macroscopic properties, but also provide valuable guidance for the design and engineering of advanced polymer nanocomposites, thereby enhancing the material performance through strategic molecular design.

Self-healing bottlebrush polymer networks enabled via a side-chain interlocking design.

Exploring novel healing mechanisms is a constant impetus for the development of self-healing materials. Herein, we find that side-chain interlocking of bottlebrush polymers can form a dynamic network and thereby serve as a driving force for the self-healing process of the materials. Molecular dynamics simulation indicates that the interlocking is formed by the interpenetration between the long side chains of adjacent molecules and stabilized by van der Waals interactions and molecular entanglements of side chains. The interlocking can be tailored by changing the length and density of the side chains through atom transfer radical polymerization. As a result, the optimized bottlebrush polymer shows a healing efficiency of up to 100%. Unlike chemical interactions, side-chain interlocking eliminates the introduction of specific chemical groups. Therefore, bottlebrush polymers can even self-heal under harsh aqueous conditions, including acid and alkali solutions. Moreover, the highly dynamic side-chain interlocking enables bottlebrush polymers to efficiently dissipate vibration energy, and thus they can be used as damping materials. Collectively, side-chain interlocking expands the scope of physical interactions in self-healing materials and hews out a versatile way for polymers to accomplish self-healing capability in various environments.

Optimizing the heterogeneous network structure to achieve polymer nanocomposites with excellent mechanical properties.

Designing and optimizing the polymer network structure at the molecular level to manipulate its mechanical properties are of great scientific significance. Although heterogeneous multi-network structures have been extensively investigated, little effort has been devoted to investigating heterogeneous single-networks with a well-defined interface. Herein, through coarse-grained molecular dynamics simulation, we successfully fabricated a heterogeneous single-network, which was divided into several regions with different crosslink densities. Firstly, we found that there is an optimal crosslink density ratio between high and low crosslink density regions to obtain the best stress-strain behavior. Secondly, the effect of the regularity of the network topology (by changing the distribution of two-phase regions) on mechanical properties was also studied. It was clearly observed that the polymer network showed better elastic response and mechanical properties as the distribution of two-phase regions became uniform. Finally, we investigated the effect of the selective distribution of nanoparticles (NPs) on mechanical properties by introducing NPs into a pre-designed multiphase network. Results showed that the selective distribution of NPs in the high crosslink density region had a more significant effect on the mechanical reinforcement. Generally, our simulated results may provide some guidelines to design polymer network structures to achieve high-performance polymer nanocomposites with excellent mechanical properties.