Polymer compatibility effects on morphologies from mixed brushes probed by high pressure GISANS (HP-GISANS), specular and off-specular reflectivity

By means of Grazing Incidence Small Angle Neutron Scattering under hydrostatic pressure (HP- GISANS) and neutron reflectometry at the solid-liquid interface, we compare effects of pressure and temperature on two model homopolymer mixed brush systems in thin (<100 nm) film geometry: a weakly incom...

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Autori principali: Vagias, Apostolos N. (Autore) , Manouras, Theodore (Autore) , Gutfreund, Philipp (Autore) , Le Dû, Morgan Pierre (Autore) , Koufakis, Eleftherios (Autore) , Kosbahn, David Paul (Autore) , Baier, Thomas (Autore) , Buchner, Andreas (Autore) , Wolf, Marcell (Autore) , Chiappisi, Leonardo (Autore) , Dahint, Reiner (Autore) , Vamvakaki, Maria (Autore) , Müller-Buschbaum, Peter (Autore)
Natura: Article (Journal)
Lingua:inglese
Pubblicazione: 11 June 2026
In: Polymer
Year: 2026, Volume: 357, Pages: 1-14
ISSN:1873-2291
DOI:10.1016/j.polymer.2026.130029
Accesso online:Verlag, kostenfrei, Volltext: https://doi.org/10.1016/j.polymer.2026.130029
Verlag, kostenfrei, Volltext: https://www.sciencedirect.com/science/article/pii/S0032386126004763
Testo
Note sull'autore:Apostolos Vagias, Theodore Manouras, Philipp Gutfreund, Morgan Pierre Le Dû, Eleftherios Koufakis, David Paul Kosbahn, Thomas Baier, Andreas Buchner, Marcell Wolf, Leonardo Chiappisi, Reiner Dahint, Maria Vamvakaki, Peter Müller-Buschbaum
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Riassunto:By means of Grazing Incidence Small Angle Neutron Scattering under hydrostatic pressure (HP- GISANS) and neutron reflectometry at the solid-liquid interface, we compare effects of pressure and temperature on two model homopolymer mixed brush systems in thin (<100 nm) film geometry: a weakly incompatible (poly(methyl methacrylate)/poly(2-(dimethylamino)ethyl methacrylate)) (PMMA/PDMAEMA) and strongly incompatible ((poly((2,2,3,3,4,4,5,5-octafluoro)pentyl methacrylate))/poly(2-(dimethylamino)ethyl methacrylate)) (POFPMA/PDMAEMA) one. A dual responsive, temperature and pressure-sensitive, polymer (PDMAEMA) in both systems allows to explore the role of mixing incompatibilities between tethered macromolecules with solvent and also pressure on the morphological changes in the PDMAEMA-containing nanostructures. Our findings indicate distinct pressure-dependent response in both lateral (HP-GISANS) and transversal (specular NR) nanostructure depending on the chemical composition. Specular ToF-NR results suggest that temperature effects are found to be counteracted by pressure. We conclude that mixing non-idealities and residual unoccupied volume from hydrophobic domains within the investigated mixed brushes, similar to what is anticipated for homopolymer brushes, are polymer-compatibility dependent. Moreover, pressure enhances access to such nanocavities as evidenced by enhanced D2O retention within the brush in proximal distance to the substrate by the strongly incompatible POFPMA/PDMAEMA mixed brush. GISANS analysis indicates the presence of uncorrelated cylindrical hydrophobic nanostructures within a PDMAEMA-based swollen matrix. Moreover, off-specular scattering (OSS) analysis demonstrates that the spacing between hydrophobic domains and the associated surface coverage by hydrophilic regions exhibits changes with pressure only for the strongly incompatible POFPMA/PDMAEMA mixed brush. Our HP- GISANS and off-specular scattering results suggest that the length scale of phase separation on the sample surface along the beam direction can strongly depend on the compositional variation in the mixed brushes.
Descrizione del documento:Online verfügbar: 22. April 2026, Artikelversion: 29. April 2026
Gesehen am 10.08.2026
Descrizione fisica:Online Resource
ISSN:1873-2291
DOI:10.1016/j.polymer.2026.130029