Enhanced Interfacial Bonding of Graft Copolymers

Gao, Yawei; Jayswal, Ajay; Das, Arit; Carrillo, Jan Michael Y.; Damron, Joshua T.; Bowland, Christopher C.; Yu, Zeyang; Toomey, Michael; Angelopoulou, Polyxeni P.; Kharal, Shankar; Mendis, Gamini; Humphrey, Holly; Sumpter, Bobby G.; Kearney, Logan T.; Naskar, Amit K.

doi:10.1021/acsami.5c07832

Enhanced Interfacial Bonding of Graft Copolymers

Journal Article · Fri Aug 22 04:00:00 EDT 2025 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5c07832· OSTI ID:3002230

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Pennsylvania State Univ., Erie, PA (United States). Behrend College

To understand how thermoplastic welding strength can be tuned through chemical modifications and macromolecular topology, we combined coarse-grained molecular dynamics (MD) simulations with experimental validation. Our simulations examined the diffusion dynamics of both linear and graft polymers across representative interfaces, revealing that diffusion-controlled interdigitation follows a power law, with the exponent decreasing from 0.34 to 0.11 as grafting density increases from 7.5 to 196% (with side chains grafted to both sides of a monomer unit). The addition of side chains enhances welding efficiency, as dense bottlebrush polymers with high grafting density reach maximum rupture strength faster than linear polymers. However, their saturated rupture strength is lower. This observation is subsequently corroborated by experimental lap-shear tests comparing linear polyethylene with octene grafted polyethylene elastomers. Our MD simulations show that unlike linear polymers, where backbone entanglements dominate, the grafted side chains introduce mechanisms in addition to entanglement dilution. The rapid interdigitation of side chains creates a dense mesh of entropic van der Waals contacts, which can also enhance the film welding. Furthermore, our MD simulations reveal a brittle rupture behavior in linear and comb-like (mildly grafted) polymers, while bottlebrush (densely grafted) polymers display elastomeric behavior with a pronounced stress plateau prior to fracture. Our simulations deconvolute the influence of polymer topology on deformation behavior. The rate of polymer deformation becomes lower than the applied strain rate prior to rupture, and the onset of this deviation is progressively delayed from linear to bottlebrush polymers. This trend highlights the critical role of molecular architecture in governing the mechanical response. In conclusion, these results provide deeper insight into the underlying welding mechanisms of topological polymers and present a potential approach for mitigating the interface anisotropy that is inherent in advanced manufacturing techniques such as fused filament fabrication.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 3002230

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 36 Vol. 17; ISSN 1944-8244; ISSN 1944-8252

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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