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J Colloid Interface Sci. 2018 Feb 15;512:609-617. doi: 10.1016/j.jcis.2017.10.094. Epub 2017 Oct 26.

Unveiling the hybrid interface in polymer nanocomposites enclosing silsesquioxanes with tunable molecular structure: Spectroscopic, thermal and mechanical properties.

Author information

1
Dept. of Materials Science, INSTM, University of Milano-Bicocca, Via R. Cozzi 55, 20125 Milano, Italy. Electronic address: massimiliano.darienzo@unimib.it.
2
Dept. Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, Italy; "Klaus Müller" Magnetic Resonance Lab., DII, University of Trento, via Sommarive 9, 38123 Trento, Italy. Electronic address: sandra.dire@unitn.it.
3
Dept. of Materials Science, INSTM, University of Milano-Bicocca, Via R. Cozzi 55, 20125 Milano, Italy.
4
Dept. Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, Italy.
5
Dept. Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, Italy; "Klaus Müller" Magnetic Resonance Lab., DII, University of Trento, via Sommarive 9, 38123 Trento, Italy.

Abstract

Organic-inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs.

KEYWORDS:

Hybrid materials; Interfaces; Mechanical properties; Nanobuilding blocks; Nanocomposite; Silsesquioxanes

PMID:
29101902
DOI:
10.1016/j.jcis.2017.10.094

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