Supramolecular Superparamagnetic Nanocomposites Based on a Magnetite-Filled Unentangled Terpyridine-Functionalized Polymer

Falco, Guillaume; Griffiths, Pablo; Coutouly, Clément; Fustin, Charles‐André; Baeza, Guilhem P.

doi:10.1021/acs.macromol.0c00182

Cited by 5 publications

(12 citation statements)

References 51 publications

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“…Random copolymerization of n-BA and terpyridine functionalized monomer was performed by reversible addition−fragmentation chain transfer polymerization (RAFT) under bulk conditions at 70 °C using 2-(dodecylthiocarbonothioylthio)-2methylpropionic acid (DDMAT) as RAFT agent following a previously reported procedure. 11 Briefly, AIBN (3 mg, 18.3 μmol), DDMAT (44.5 mg, 0.122 mmol), n-BA (3.37 mL, 23.8 mmol), and acrylate-TPy (535 mg, 1.44 mmol) were introduced into a 10 mL Schlenk tube. After the solution was degassed by six freeze−pump− thaw cycles, the reaction mixture was sealed, purged with argon, and then immersed in a preheated oil bath at 70 °C.…”

Section: Methodsmentioning

confidence: 99%

Magneto-Responsive Nanocomposites with a Metal–Ligand Supramolecular Matrix

et al. 2022

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Magneto-responsive nanocomposites are prepared by mixing 1−5 vol % of Fe nanoparticles (NPs) in a metallo-supramolecular network made of poly(n-butyl acrylate) (PnBA) bearing terpyridine side groups and cross-linked by the addition of different amounts of Zn 2+ ions. To have a clear understanding of the stepwise increase of complexity, the thermomechanical behavior of these materials was characterized through shear linear rheology at each step of their preparation. The metallo-supramolecular networks reveal a clear transition from polymer-to network-driven dynamics when passing progressively from low (<0 °C) to high temperature. While terpyridine (TPy)−Zn 2+ complexes are usually treated as independent "stickers", the analysis of our master curves strongly suggests their aggregation. After the addition of 1−5 vol % of Fe nanoparticles within the supramolecular networks, we evidence the presence of TPy−NP bonds, resulting in a hybrid network of much longer relaxation time. Lastly, we combine thermal imaging and induction heating to emphasize the signature of sticker dissociation, offering new technical solutions to deepen our fundamental understanding of supramolecular networks.

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Section: Methodsmentioning

confidence: 99%

Magneto-Responsive Nanocomposites with a Metal–Ligand Supramolecular Matrix

et al. 2022

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“…Alternatively, Ramanujan et al developed promising healable rubbers based on copolymers (either polyethylene–vinyl acetate or acrylonitrile butadiene), , but the lack of systematic physical characterization inhibits the adaptation of the concept to more conventional, that is, industry-oriented, chemistries. Alternatively, several research groups attempted to control the solid-to-liquid transition in model supramolecular networks through induction heating. − In these examples, ionic aggregates, terpyridine, and ureidopyrimidinone moieties were, respectively, used, without providing strong mechanical properties to the materials, which displayed a shear modulus below 1 MPa or a flow regime at room temperature. Importantly, all the above-mentioned materials (excluding ref ) were prepared through solvent casting, precluding large-scale production.…”

Section: Introductionmentioning

confidence: 99%

“…Alternatively, several research groups attempted to control the solid-to-liquid transition in model supramolecular networks through induction heating. − In these examples, ionic aggregates, terpyridine, and ureidopyrimidinone moieties were, respectively, used, without providing strong mechanical properties to the materials, which displayed a shear modulus below 1 MPa or a flow regime at room temperature. Importantly, all the above-mentioned materials (excluding ref ) were prepared through solvent casting, precluding large-scale production. In summary, although magneto-responsive thermoplastic rubbers are henceforth quite popular to serve as actuators, − it appears that triggering their phase transition in view of a possible healing or post-processing treatment remains a largely uncharted territory, limited to the field of adhesives , and bioengineering-oriented hydrogels .…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Remote Healing of Magneto-Responsive Thermoplastic Elastomer-Based Nanocomposites

et al. 2022

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We describe herein, a general, efficient, and scalable process to design magneto-responsive thermoplastic elastomer-based (nano)composites that can be repeatedly healed in a few tens of seconds by triggering polymer melting upon exposure to a high-frequency magnetic field. Three series of composites loaded with 1–15 vol % of Fe3O4 nanoparticles, Fe nanoparticles, or Fe microparticles were produced and characterized in depth with the aim to identify the physical properties required for two applications: (1) material healing, which we evaluate through the rewelding of precut samples and subsequent tensile tests, and (2) surface smoothening of 3D-printed objects, serving to remove superficial defects and improve their appearance. The optimal formulation consisting of a composite reinforced with 5 vol % of Fe nanoparticles ensures a high ability to heat while keeping a low viscosity in the molten state being ideal for polymer processing.

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“…[19][20][21][22] Surface ligands that interact with the polymer matrix through hydrogen bonding or other attractive interactions can serve as transient physical crosslinks that increase the overall modulus of the composite structure. [23][24][25][26][27] The long-range order of microphase separated BCPs dominates the viscoelasticity and rheological properties at long time scales. 28 Specifically in BBCPs, the dense grafting of side chains suppresses chain entanglements in the melt state, resulting in highly mobile "liquid-like" rheology.…”

Section: Introductionmentioning

confidence: 99%

“…NPs are also much stiffer than the polymer matrix and can enhance the mechanical properties through structural percolation or topological constraints on the polymer chains 19–22 . Surface ligands that interact with the polymer matrix through hydrogen bonding or other attractive interactions can serve as transient physical crosslinks that increase the overall modulus of the composite structure 23–27 …”

Section: Introductionmentioning

confidence: 99%

Liquid‐to‐solid transitions in nanoparticle‐filled brush block copolymer composites

Yavitt

Fei

Kopanati

et al. 2020

Journal of Polymer Science

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The natural self-assembly of densely grafted brush block copolymers (BBCP) is used to direct functional nanoparticles (NP) into well-ordered structures with large lattice spacings and high NP content. Understanding the NP's impact on the phase behavior and viscoelastic properties is necessary for optimizing the processing windows for such materials. Thermo-structural and thermorheological properties are investigated in a model nanocomposite system composed of a di-block bottlebrush (dbBB) poly(tert-butyl acrylate)-block-poly(ethylene oxide) (PtBA-b-PEO), complexed with surface functionalized zirconium oxide (ZrO 2) NPs. The NPs selectively sequester into the microphase separated PEO domains through coordinated hydrogen bonding. Loading up to φ = 30 wt% NP is achieved, and the lamellar morphologies are stable in the melt state according to temperature controlled small angle X-ray scattering (SAXS). Systematic transitions in the linear viscoelasticity, determined by small amplitude oscillatory shear (SAOS) suggest that at slow timescales, the NP superstructure inhibits the highly mobile relaxation processes inherent to the dbBB architecture. Further analysis of the relaxation time spectrum H(τ) is used to describe the constraint of such relaxation mechanisms. The structureproperty relationships realized by SAOS and SAXS enable future manipulation of mechanical properties and processing of BBCP/NP composites for both established and emergent applications.

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Supramolecular Superparamagnetic Nanocomposites Based on a Magnetite-Filled Unentangled Terpyridine-Functionalized Polymer

Cited by 5 publications

References 51 publications

Magneto-Responsive Nanocomposites with a Metal–Ligand Supramolecular Matrix

Magneto-Responsive Nanocomposites with a Metal–Ligand Supramolecular Matrix

Ultrafast Remote Healing of Magneto-Responsive Thermoplastic Elastomer-Based Nanocomposites

Liquid‐to‐solid transitions in nanoparticle‐filled brush block copolymer composites

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