Interesting Facets of Surface, Interfacial, and Bulk Characteristics of Perfluorinated Ionomer Films
Notice bibliographique
Résumé
Ion-containing perfluorinated polymers possess unique viscoelastic properties, excellent proton conductivity, and nanophase-segregated structure all arising from the clustering of hydrophilic sulfonic acid groups within a matrix of hydrophobic fluorocarbons. When these ionomers are confined to nanothin films, a broad swathe of structural organization imparting a rich variety of surface, interfacial, and bulk characteristics can be expected. However, our understanding of perfluorinated ionomer thin film behavior is still in a rudimentary stage, and much of the research focus to date has been on its hydration-related structure and properties pertinent to electrochemical applications. Thus, many hidden gems-their interesting surface and interfacial properties-have been overlooked. In this Invited Feature Article, which is a summary of the key contributions by the author's group, including several collaborative publications on ionomer thin films, we unravel many of these facets. In addition, the article attempts to integrate knowledge acquired from a variety of investigations of different aspects of the ionomer thin films to refine and develop a consistent picture of their structure and behavior. First, we focus on the self-assembly of ionomers and show that dispersion media and hydrophobicity/hydrophilicity of the substrate can result in partial or even no coverage of substrates, shedding light on the complexity of polymer-substrate, polymer-solvent, and polymer-polymer interactions, an insight completely obscured when the spin-coating method is adopted for film creation. We demonstrate that the same ionomer can be used to create a variety of surfaces ranging from superhydrophilic to highly hydrophobic by controlling the film thickness or through the choice of substrate material. The ultrathin, hydrophilic surfaces of self-assembled Nafion ionomer films exhibit wettability switching behavior which opens the door to creating stimuli-responsive smart surfaces. The thermoresponsive behavior of the films is discussed in the context of surface (wettability) and bulk (thermal expansion) characteristics as well as a newly discovered vibrational mode. The substrate- and film thickness-dependent thermal expansion coefficients reinforce the importance of interfacial interactions and confinement on the structure/properties of these films. They also open up the potential of tuning ionomer bulk properties via substrate chemistry. The discovery of a vibrational mode that becomes thermally activated at high temperature has provided new insights into the origins of the molecular motions responsible for the α-relaxation of the Nafion ionomer as well as the underlying reason for wettability switching. Our recent neutron reflectometry study of different ionomers varying in side-chain composition/length on a platinum substrate shows that the interfacial hydration level is correlated to the side-chain length, which opens up the possibility of the controlling the interfacial electrochemistry. Finally, a systematic analysis of factors affecting proton conduction is presented to elucidate the yet-unresolved origins of the suppressed conduction of nanothin ionomer films compared to that of the bulk membrane. By revealing these interesting yet poorly understood facets of ionomer thin films, the article aims to stimulate further scientific pursuit on this topic.
Récupéré en direct depuis OpenAlex et désinversé. Les résumés ne sont pas conservés dans cette base de données : les index inversés représentent 8,6 Go des 9,3 Go de texte de la base, et le serveur dispose de 13 Go libres.
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Prédiction distillée sur la base complète
Imitation des enseignantsNi prévalence calibrée, ni vérité terrain. Validation humaine à venir. Apprise à partir de 10 348 étiquettes directes de Codex et de 10 348 étiquettes directes de Gemma. Le mode candidate est l'union des têtes enseignantes seuillées; le consensus est leur intersection. Ces sorties portent le statut machine_predicted_unvalidated et ne sont ni des étiquettes humaines ni des étiquettes directes de modèles de pointe.
Scores Codex et Gemma par catégorie
| Catégorie | Codex | Gemma |
|---|---|---|
| Métarecherche | 0,000 | 0,000 |
| Méta-épidémiologie (sens strict) | 0,000 | 0,000 |
| Méta-épidémiologie (sens large) | 0,000 | 0,000 |
| Bibliométrie | 0,000 | 0,000 |
| Études des sciences et des technologies | 0,000 | 0,000 |
| Communication savante | 0,000 | 0,000 |
| Science ouverte | 0,000 | 0,000 |
| Intégrité de la recherche | 0,000 | 0,000 |
| Charge utile insuffisante (le modèle a refusé de juger) | 0,000 | 0,000 |
Scores machine (provisoires)
Les deux têtes enseignantes du modèle étudiant, lues sur ce travail. Un score ordonne la base pour la relecture; il n'affirme jamais une catégorie, et le statut de validation accompagne chaque rangée tel quel.
Scores de référence d'un modèle non mature (critères de maturité non atteints, 7 itérations). Un score ordonne; il n'affirme jamais une catégorie.
score_only:v0-immature-baseline · tel quel depuis la passe de notation : score_only signifie que le nombre peut ordonner les travaux, et qu'aucune étiquette de catégorie n'en découleClassification
machine, non validéePrédiction automatique; un appel candidat d’une seule tête enseignante, pas un consensus.
Le détail, modèle par modèle et score par score, se trouve en fin de page sous « Comment cette classification a été obtenue ».