Naturally occurring nanocomposites like nacre owe their exceptional mechanical properties to high loadings of platelets that are bridged by small volume fractions of polymers. Polymer infiltration into dense assemblies of nanoparticles provides a powerful and potentially scalable approach to manufacture bio-inspired nanocomposites that mimic nacre's architecture. Solvent-driven infiltration of polymers (SIP) into nanoparticle packings formed on top of glassy polymer films is induced via capillary condensation of a solvent in the interstitial voids between nanoparticles (NP), followed by plasticization and transport of polymers into the liquid-filled pores, leading to the formation of the nanocomposite structure. To understand the effect of polymer–nanoparticle interactions on the dynamics of polymer infiltration in SIP, we perform molecular dynamics simulations. The mechanism of polymer infiltration and the influence of interactions between polymer and NPs on the dynamics of the process are investigated. Depending on the strength of interaction, polymer infiltration either follows (a) dissolution-dominated infiltration where plasticized polymer chains remain solvated in the pores and rapidly diffuse into the packing or (b) adhesion-dominated transport where the chains adsorb onto the nanoparticle surface and move slowly through the nanoparticle film as a well-defined front. A non-monotonic trend emerges as the adhesion strength is increased; the infiltration of chains becomes faster with the co-operative effect of adhesion and dissolution as adhesion increases but eventually slows down when the polymer–nanoparticle adhesion dominates.
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Effects of polymer–nanoparticle interactions on the viscosity of unentangled polymers under extreme nanoconfinement during capillary rise infiltration
We explore the effect of confinement and polymer–nanoparticle interactions on the viscosity of unentangled polymers undergoing capillary rise infiltration (CaRI) in dense packings of nanoparticles. In CaRI, a polymer is thermally induced to wick into the dense packings of nanoparticles, leading to the formation of polymer-infiltrated nanoparticle films, a new class of thin film nanocomposites with extremely high concentrations of nanoparticles. To understand the effect of this extreme nanoconfinement, as well as polymer–nanoparticle interactions on the polymer viscosity in CaRI films, we use two polymers that are known to have very different interactions with SiO 2 nanoparticles. Using in situ spectroscopic ellipsometry, we monitor the polymer infiltration process, from which we infer the polymer viscosity based on the Lucas–Washburn model. Our results suggest that physical confinement increases the viscosity by approximately two orders of magnitude. Furthermore, confinement also increases the glass transition temperature of both polymers. Thus, under extreme nanoconfinement, the physical confinement has a more significant impact than the polymer–nanoparticle interactions on the viscosity of unentangled polymers, measured through infiltration dynamics, as well as the glass transition temperature. These findings will provide fundamental frameworks for designing processes to enable the fabrication of CaRI nanocomposite films with a wide range of nanoparticles and polymers.
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- Award ID(s):
- 1662695
- PAR ID:
- 10099037
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 14
- Issue:
- 13
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 2438 to 2446
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Polymer‐infiltrated nanoparticle films (PINFs) that have high volume fractions (>50 vol%) of nanoparticles (NPs) possess enhanced properties making them ideal for various applications. Capillary rise infiltration (CaRI) of polymer and solvent‐driven infiltration of polymer (SIP) into pre‐assembled NP films have emerged as versatile approaches to fabricate PINFs. Although these methods are ideal for fabricating PINFs with homogenous structure, several applications including separations, and photonic/optical coatings would benefit from a method that enables scalable manufacturing of heterostructured (i.e., films with variation in structural properties such as porosity, composition, refractive indices, etc.) PINFs. In this work, a new technique is developed for fabricating heterostructured PINFs with cavities based on CaRI. A bilayer composed of densely packed inorganic NP layer atop polymer NP layer is thermally annealed above the glass transition temperature of the polymer NP, which induces CaRI of the polymer into the interstices of the inorganic NP layer. Exploiting the difference in the sizes of the two particles, heterostructured double stack PINFs composed of a PINF and a layer with large cavities are produced at a moderate temperature (<200 °C). Using these heterostructured PINFs, Bragg reflectors that can detect the presence of wetting agents in water are fabricated.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c7sm02465g
