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.
Polymer blend-filled nanoparticle films via monomer-driven infiltration of polymer and photopolymerization
Incorporation of nanoparticles into polymer blend films can lead to a synergistic combination of properties and functionalities. Adding a large concentration of nanoparticles into a polymer blend matrix via conventional melting or solution blending techniques, however, is challenging due to the tendency of particles to aggregate. Herein, we report a straightforward approach to generate polymer blend/nanoparticle ternary composite films with extremely high loadings of nanoparticles based on monomer-driven infiltration of polymer and photopolymerization. The fabrication process consists of three steps: (1) preparing a bilayer with a nanoparticle (NP) layer atop a polymer layer, (2) annealing of the bilayer with a vapour mixture of a monomer and a photoinitiator, which undergoes capillary condensation and imparts mobility to the polymer layer and (3) exposing this film to UV light to induce photopolymerization of the monomer. The monomer used in this process is chemically different from the repeat unit of the polymer in the bilayer and is a good solvent for the polymer. The second step leads to the infiltration of the plasticized polymer, and the third step results in a blend of two polymers in the interstices of the nanoparticle layer. By varying the thickness ratio of the polymer and nanoparticle layers in the initial bilayers and changing the UV exposure duration, the volume fraction of the two polymers in the composite films can be adjusted. This versatile approach enables the design and engineering of a new class of nanocomposite films that contain a nanoscale-blend of two polymers in the interstices of a nanoparticle film, which could have combinations of unique mechanical and transport properties desirable for advanced applications such as membrane separations, conductive composite films and solar cells. Moreover, these polymer blend-filled nanoparticle films could serve as model systems to study the effect of confinement on the miscibility and morphology of polymer blends.
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- Award ID(s):
- 1662695
- NSF-PAR ID:
- 10058531
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- Volume:
- 3
- Issue:
- 1
- ISSN:
- 2058-9689
- Page Range / eLocation ID:
- 96 to 102
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
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.more » « less
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null (Ed.)Alignment of highly anisotropic nanomaterials in a polymer matrix can yield nanocomposites with unique mechanical and transport properties. Conventional methods of nanocomposite film fabrication are not well-suited for manufacturing composites with very high concentrations of anisotropic nanomaterials, potentially limiting the widespread implementation of these useful structures. In this work, we present a scalable approach to fabricate polymer-infiltrated nanoplatelet films (PINFs) based on flow coating and capillary rise infiltration (CaRI) and study the processing–structure–property relationship of these PINFs. We show that films with high aspect ratio (AR) gibbsite (Al (OH) 3 ) nanoplatelets (NPTs) aligned parallel to the substrate can be prepared using a flow coating process. NPTs are highly aligned with a Herman's order parameter of 0.96 and a high packing fraction >80 vol%. Such packings show significantly higher fracture toughness compared to low AR nanoparticle (NP) packings. By depositing NPTs on a polymer film and subsequently annealing the bilayer above the glass transition temperature of the polymer, polymer infiltrates into the tortuous NPT packings though capillarity. We observe larger enhancement in the modulus, hardness and scratch resistance of NPT films upon polymer infiltration compared to NP packings. The excellent mechanical properties of such films benefit from both thermally promoted oxide bridge formation between NPTs as well as polymer infiltration increasing the strength of NPT contacts. Our approach is widely applicable to highly anisotropic nanomaterials and allows the generation of mechanically robust polymer nanocomposite films for a diverse set of applications.more » « less
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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.more » « less
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Ultraviolet (UV) printing of photopolymers is a widely adopted manufacturing method because of its high resolution and throughput. However, available printable photopolymers are typically thermosets, resulting in challenges in postprocessing and recycling of printed structures. Here, we present a new process called interfacial photopolymerization (IPP) which enables photopolymerization printing of linear chain polymers. In IPP, a polymer film is formed at the interface between two immiscible liquids, one containing a chain-growth monomer and the other containing a photoinitiator. We demonstrate the integration of IPP in a proof-of-concept projection system for printing of polyacrylonitrile (PAN) films and rudimentary multi-layer shapes . IPP shows in-plane and out-of-plane resolutions comparable to conventional photoprinting methods. Cohesive PAN films with number-average molecular weights greater than 15 kg mol–1 are obtained, and to our knowledge this is the first report of photopolymerization printing of PAN. A macrokinetics model of IPP is developed to elucidate the transport and reaction rates involved and evaluate how reaction parameters affect film thickness and print speed. Last, demonstration of IPP in a multilayer scheme suggests its suitabiliy for three-dimensional printing of linear-chain polymers.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C7ME00099E
