Self‐healing Polymers through Dynamic Covalent Chemistry

Imato, Keiichi; Otsuka, Hideyuki

doi:10.1002/9781119075738.ch9

Cited by 15 publications

(14 citation statements)

References 155 publications

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“…Analogous breaking of DCB-crosslinked polymer networks 43,45 has been demonstrated by introducing a small molecule that displaced the bonded functional groups on neighboring polymer chains. 47,48,100,101 In our linked NC gels, the capping molecule MH disrupted the network, recovering a free-flowing dispersion. SAXS revealed that the gel reversal process did not result in a dispersion of completely discrete NCs.…”

Section: Ligandmentioning

confidence: 89%

“…28,29,[38][39][40]46 The reversibility of DCB has been used to create selfhealing, responsive, and reconfigurable polymer networks, whose cross-links are dynamic. 44,45,47,48 When used to mediate attractions between NCs, DCB is expected to favor structures that tend toward equilibrium rather than becoming kinetically arrested, allowing thermodynamic principles to be leveraged to predict and design the phase behavior of NC assemblies. DCB has been incorporated in direct NC-to-NC bonding strategies using metal NCs functionalized with ligands bearing complementary DCB pairs, and these assemblies were shown to be reversible with the introduction of a competing molecule.…”

Section: Introductionmentioning

confidence: 99%

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Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

et al. 2020

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The use of dynamically bonding molecules designed to reversibly link solvent-dispersed nanocrystals (NCs) is a promising strategy to form colloidal assemblies with controlled structure and macroscopic properties. In this work, tin-doped indium oxide NCs are functionalized with ligands that form reversible covalent bonds with linking molecules to drive assembly of NC gels. We monitor gelation using small angle X-ray scattering and characterize how changes in the gel structure affect infrared optical properties arising from the localized surface plasmon resonance of the NCs. The assembly is reversible because of the designed linking chemistry, and we disassemble the gels using two strategies: addition of excess NCs to change the ratio of linking molecules to NCs and addition of a capping molecule that displacesthe linking molecules. The assembly behavior is rationalized using a thermodynamic perturbation theory to compute the phase diagram of the NC-linking molecule mixture. Coarse-grained molecular dynamics simulations reveal the competition between loop and bridge linking motifs essential for understanding NC gelation. This combined experimental, computational, and theoretical work provides a platform for controlling and designing the properties of reversible colloidal assemblies that incorporate NC and solvent compositions beyond those compatible with other contemporary (e.g, DNA-based) linking strategies. File list (2) download file view on ChemRxiv Manuscript.pdf (3.07 MiB) download file view on ChemRxiv Supporting Information.pdf (2.48 MiB)

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Section: Ligandmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

et al. 2020

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“…Many reviews, communications and book chapters on the state-of-the-art of self-healing and healable polymers, PMCs and FRPCs have been published [ 1 , 3 , 4 , 6 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ], and some of them are indeed recent [ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ]. This review focuses exclusively on the description of the main intrinsic self-healing epoxy systems found in the literature, both as a standalone material and as matrices in PMCs, with an emphasis on those systems that are particularly suitable for aerospace applications.…”

Section: Introductionmentioning

confidence: 99%

Intrinsic Self-Healing Epoxies in Polymer Matrix Composites (PMCs) for Aerospace Applications

et al. 2021

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This article reviews some of the intrinsic self-healing epoxy materials that have been investigated throughout the course of the last twenty years. Emphasis is placed on those formulations suitable for the design of high-performance composites to be employed in the aerospace field. A brief introduction is given on the advantages of intrinsic self-healing polymers over extrinsic counterparts and of epoxies over other thermosetting systems. After a general description of the testing procedures adopted for the evaluation of the healing efficiency and the required features for a smooth implementation of such materials in the industry, different self-healing mechanisms, arising from either physical or chemical interactions, are detailed. The presented formulations are critically reviewed, comparing major strengths and weaknesses of their healing mechanisms, underlining the inherent structural polymer properties that may affect the healing phenomena. As many self-healing chemistries already provide the fundamental aspects for recyclability and reprocessability of thermosets, which have been historically thought as a critical issue, perspective trends of a circular economy for self-healing polymers are discussed along with their possible advances and challenges. This may open up the opportunity for a totally reconfigured landscape in composite manufacturing, with the net benefits of overall cost reduction and less waste. Some general drawbacks are also laid out along with some potential countermeasures to overcome or limit their impact. Finally, present and future applications in the aviation and space fields are portrayed.

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Section: Introductionmentioning

confidence: 99%

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Domínguez

Howard²,

Maier³

et al. 2020

Preprint

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<div>The use of dynamically bonding molecules designed to reversibly link solvent-dispersed nanocrystals (NCs) is a promising strategy to form colloidal assemblies with controlled structure and macroscopic properties. In this work, tin-doped indium oxide NCs are functionalized with ligands that form reversible covalent bonds with linking molecules to drive assembly of NC gels. We monitor gelation using small angle X-ray scattering and characterize how changes in the gel structure affect infrared optical properties arising from the localized surface plasmon resonance of the NCs. The assembly is reversible because of the designed linking chemistry, and we disassemble the gels using two strategies: addition of excess NCs to change the ratio of linking molecules to NCs and addition of a capping molecule that displaces</div><div>the linking molecules. The assembly behavior is rationalized using a thermodynamic perturbation theory to compute the phase diagram of the NC–linking molecule mixture. Coarse-grained molecular dynamics simulations reveal the competition between loop and bridge linking motifs essential for understanding NC gelation. This combined experimental, computational, and theoretical work provides a platform for controlling and designing the properties of reversible colloidal assemblies that incorporate NC and solvent compositions beyond those compatible with other contemporary (e.g, DNA-based) linking strategies.</div>

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Self‐healing Polymers through Dynamic Covalent Chemistry

Cited by 15 publications

References 155 publications

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Intrinsic Self-Healing Epoxies in Polymer Matrix Composites (PMCs) for Aerospace Applications

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

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