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We employ molecular dynamics (MD) simulations to investigate the mechanical behaviors of immiscible polymer interfaces enhanced by block copolymer compatibilizers. We show that the entanglement density at the interface, governed by the Flory–Huggins parameter χ, is critical for mechanical performance. Increasing immiscibility leads to sharper interfaces with reduced interfacial entanglements, resulting in easy chain pullout during tensile deformation and weaker interfacial strength. Adding block copolymer compatibilizers to the blends can switch the failure mechanism from interfacial chain pullout to bulk-phase crazing, substantially enhancing mechanical performance. Although long diblock and tetrablock copolymers only mildly increase the interfacial entanglement density, they can act as stress transmitters across the interface by entangling with chains in the bulk domains. Tetrablock copolymers are particularly effective for strengthening polymer blends by forming loops at the interface, making chain pullout topologically more difficult and promoting energy dissipation through crazing in the bulk regions. Our findings reveal the roles of both entanglement at interfaces and block copolymer architecture in the mechanical properties of immiscible polymer interfaces, which may guide the design of better compatibilizers for enhancing inhomogeneous polymer samples.
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This content will become publicly available on April 1, 2026
Molecular Dynamics of a Polymer Blend Model on a Solid Substrate
We performed extensive molecular dynamics simulations using a bead–spring model to investigate the interfacial behavior of blends of linear and cyclic polymer chains confined between two planar, attractive substrates. The model system was studied over a range of chain lengths spanning an order of magnitude in the number of beads for varying blend compositions and for two different levels of substrate affinity. For short chains, we observed the preferential adsorption of linear chains at the substrate interface when they are the majority component (10% cyclic chains) as well as at equimolar composition. In contrast, for longer chains, cyclic chains are preferentially enriched at the interface. These results extend recent findings from neutron reflectivity experiments—where the enrichment of cyclic polystyrene chains at low-energy surfaces was demonstrated—to systems under solid confinement, providing deeper insight into the structural behavior of topologically distinct polymers near interfaces. This work highlights the potential for tuning interfacial composition and properties in polymer blends through topological design, with implications for advanced coatings, membranes, and nanostructured materials.
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- Award ID(s):
- 2114640
- PAR ID:
- 10611837
- Publisher / Repository:
- Molecules
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 30
- Issue:
- 8
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 1734
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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