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Abstract Polymer‐brush‐grafted nanoparticles (PGNPs) that can be covalently crosslinked post‐processing enable the fabrication of mechanically robust and chemically stable polymer nanocomposites with high inorganic filler content. Modifying PGNP brushes to append UV‐activated crosslinkers along the polymer chains would permit a modular crosslinking strategy applicable to a diverse range of nanocomposite compositions. Further, light‐activated crosslinking reactions enable spatial control of crosslink density to program intentionally inhomogeneous mechanical responses. Here, a method of synthesizing composites using UV‐crosslinkable brush‐coated nanoparticles (referred to as UV‐XNPs) is introduced that can be applied to various monomer compositions by incorporating photoinitiators into the polymer brushes. UV crosslinking of processed UV‐XNP structures can increase their tensile modulus up to 15‐fold without any noticeable alteration to their appearance or shape. By using photomasks to alter UV intensity across a sample, intentionally designed inhomogeneities in crosslink density result in predetermined anisotropic shape changes under strain. This unique capability of UV‐XNP materials is applied to stiffness‐patterned flexible electronic substrates that prevent the delamination of rigid components under deformation. The potential of UV‐XNPs as functional, soft device components is further demonstrated by wearable devices that can be modified post‐fabrication to customize their performance, permitting the ability to add functionality to existing device architectures.
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Forming Covalent Crosslinks between Polymer‐Grafted Nanoparticles as a Route to Highly Filled and Mechanically Robust Nanocomposites
Abstract Filler aggregation in polymer matrix nanocomposites leads to inhomogeneity in particle distribution and deterioration of mechanical properties. The use of polymer‐grafted nanoparticles (PGNPs) with polymers directly attached to the particle surfaces precludes aggregation of the filler. However, solids composed of PGNPs are mechanically weak unless the grafted chains are long enough to form entanglements between particles, and requiring long grafts limits the achievable filler density of the nanocomposite. In this work, long, entangled grafts are replaced with short reactive polymers that form covalent crosslinks between particles. Crosslinkable PGNPs, referred to as XNPs, can be easily processed from solution and subsequently cured to yield a highly filled yet mechanically robust composite. In this specific instance, silica nanoparticles are grafted with poly(glycidyl methacrylate), cast into films, and crosslinked with multifunctional amines at elevated temperatures. Indentation and scratch experiments show significant enhancement of hardness, modulus, and scratch resistance compared to non‐crosslinked PGNPs and to crosslinked polymer films without nanoparticle reinforcement. Loadings of up to 57 wt% are achieved while yielding uniform films that deform locally in a predominantly elastic manner. XNPs therefore potentially allow for the formulation of robust nanocomposites with a high level of functionality imparted by the selected filler particles.
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- Award ID(s):
- 1653289
- PAR ID:
- 10460335
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 29
- Issue:
- 44
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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