Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics

Genix, Anne-Caroline; Bocharova, Vera; Carroll, Bobby; Dieudonné-George, Philippe; Chauveau, Edouard; Sokolov, Alexei P.; Oberdisse, Julian

doi:10.3390/nano13040748

Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics

Journal Article · Wed Feb 15 23:00:00 EST 2023 · Nanomaterials

DOI:https://doi.org/10.3390/nano13040748· OSTI ID:2471470

Genix, Anne-Caroline ^[1]; Bocharova, Vera ^[2]; Carroll, Bobby ^[3]; ^[1]; Chauveau, Edouard ^[1]; ^[4]; Oberdisse, Julian ^[1]

Université de Montpellier (France)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
University of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)

Both the dispersion state of nanoparticles (NPs) within polymer nanocomposites (PNCs) and the dynamical state of the polymer altered by the presence of the NP/polymer interfaces have a strong impact on the macroscopic properties of PNCs. In particular, mechanical properties are strongly affected by percolation of hard phases, which may be NP networks, dynamically modified polymer regions, or combinations of both. In this article, the impact on dispersion and dynamics of surface modification of the NPs by short monomethoxysilanes with eight carbons in the alkyl part (C₈) is studied. As a function of grafting density and particle content, polymer dynamics is followed by broadband dielectric spectroscopy and analyzed by an interfacial layer model, whereas the particle dispersion is investigated by small-angle X-ray scattering and analyzed by reverse Monte Carlo simulations. NP dispersions are found to be destabilized only at the highest grafting. The interfacial layer formalism allows the clear identification of the volume fraction of interfacial polymer, with its characteristic time. The strongest dynamical slow-down in the polymer is found for unmodified NPs, while grafting weakens this effect progressively. The combination of all three techniques enables a unique measurement of the true thickness of the interfacial layer, which is ca. 5 nm. Finally, the comparison between longer (C₁₈) and shorter (C₈) grafts provides unprecedented insight into the efficacy and tunability of surface modification. It is shown that C₈-grafting allows for a more progressive tuning, which goes beyond a pure mass effect.

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); French Agence Nationale de la Recherche; National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2471470

Journal Information:: Nanomaterials, Journal Name: Nanomaterials Journal Issue: 4 Vol. 13; ISSN 2079-4991

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics

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