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(3) Production(s) de l'année 2023

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How Tuning Interfaces Impacts the Dynamics and Structure of Polymer Nanocomposites Simultaneously 
Auteur(s): Genix A.-C. , Bocharova Vera, Carroll Bobby, Dieudonne-George P., Chauveau E., Sokolov Alexei p., Oberdisse J.
(Article) Publié:
Acs Appl. Mater. Interfaces, vol. 15 p.7496–7510 (2023)
DOI: 10.1021/acsami.2c18083
WoS: WOS:000924061800001
Résumé: Fundamental understanding of the macroscopic properties of polymer nanocomposites (PNCs) remains difficult due to the complex interplay of microscopic dynamics and structure, namely interfacial layer relaxations and three-dimensional nanoparticle (NP) arrangements. The effect of surface modification by alkyl methoxysilanes at different grafting densities has been studied in PNCs made of poly(2-vinylpyridine) and spherical 20 nm silica NPs. The segmental dynamics has been probed by broadband dielectric spectroscopy and the filler structure by small-angle X-ray scattering and reverse Monte Carlo simulations. By combining the particle configurations with the interfacial layer properties, it is shown how surface modification tunes the attractive polymer–particle interactions: bare NPs slow down the polymer interfacial layer dynamics over a thickness of ca. 5 nm, while grafting screens these interactions. Our analysis of interparticle spacings and segmental dynamics provides unprecedented insights into the effect of surface modification on the main characteristics of PNCs: particle interactions and polymer interfacial layers.
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Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics 
Auteur(s): Genix A.-C. , Bocharova Vera, Carroll Bobby, Dieudonne-George P., Chauveau E., Sokolov Alexei p., Oberdisse J.
(Article) Publié:
Nanomaterials, vol. 13 p.748 (2023)
DOI: 10.3390/nano13040748
WoS: WOS:000941025800001
Résumé: 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.
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Polar nematic phase in short-chained fluorinated hydrogen-bonded liquid crystals 
Auteur(s): Fouzai Malek, Dieudonne-George P., Guesmi Ahlem, Ben Hamadi Naoufel, Arfaoui Youssef, Soltani Taoufik, Chevalier Yves
(Article) Publié:
Journal Of Molecular Liquids, vol. 375 p.121307 (2023)
Ref HAL: hal-03978339_v1
DOI: 10.1016/j.molliq.2023.121307
Exporter : BibTex | endNote
Résumé: So as to investigate structure-activity relationships in hydrogen bonded liquid crystals, a new short-chained (7 carbon atoms) fluorinated hydrogen-bonded liquid crystal 4-heptyloxy-2-fluorobenzoic acid, 7OBAF, is prepared. Differential scanning calorimetry, polarized optical microscopy and X-ray diffraction disclose a phase sequence as two crystalline, a nematic and the isotropic phases. Dielectric spectroscopy of the nematic phase in the frequency range of 1 Hz–6 MHz reveals a low frequency mode ascribed to ferroelectric clusters. A high polarization is induced by an external electric field, in agreement with results of dielectric measurements. Such polarization increases as the alkyl chain length is shorter. Results of DFT calculations using the Maier–Meier relationship are consistent with the dielectric measurements; they reveal the parallel molecular distribution and provide the dipole moment, polarization anisotropy, birefringence and dielectric anisotropy. Intermolecular hydrogen bonds linking the fluorine substituent and the aromatic hydrogen atoms are also disclosed.
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