Journal Article

PUBDB-2026-01354

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Entropic and Enthalpic Control of Interfacial Nanoparticle Jamming in Immiscible Polymers

Biswas, A.Extern* ; Das, N.Extern* ; Swain, A. ; Das Anthuparambil, N.Extern* ; Mendez, N. F. ; Westermeier, F.XFEL.EU*DESY* ; Kumar, S. K. ; Basu, J. (Corresponding author)Extern*

2026
ACS Washington, DC

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Please use a persistent id in citations: doi:10.1021/acsmacrolett.6c00117  doi:10.3204/PUBDB-2026-01354

Abstract: The localization of polymer grafted nanoparticles (GNPs) at the interface betweenimmiscible polymers can significantly alter their phase separation kinetics. However,modifying the role of GNP surface activity has not been explored in this context.Using in-situ atomic force microscopy and grazing-incidence X-ray photon correlationspectroscopy we reveal how subtle variations in the entropic and enthalpic interactionsbetween the GNPs and the blend polymers can result in dramatic differences in phaseseparation kinetics. We use a bilayer geometry of polystyrene (PS, molecular weight≈ 50 kDa) and poly(vinyl methyl ether) (PVME, molecular weight ≈ 80 kDa), withGNPs bearing PS chains of different molecular weights incorporated in the PS layer.While the GNPs grafted with shorter PS chains (3 kDa) should prefer the interfacedue to entropic effects, the gold GNP cores have a strong enthalpic preference for the PVME phase (even though the PS grafts themselves do not enthalpically prefer thePVME). As a result, these GNPs do not localize and jam the interface and blendsdo not show arrested phase separation. In contrast, GNPs grafted with longer PSchains (20 kDa), which do not experience such favorable enthalpic effects with thePVME due to screening of the enthalpic interactions between the core and PVME,are interfacially localized leading to a strong arrest of phase separation. These resultsestablish that the co-evolution of GNP segregation and phase separation is the decisivefactor in stabilizing polymer blends, offering a new design principle for GNP–polymercomposites under non-equilibrium conditions.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. PETRA-S (FS-PETRA-S)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
3. INDIA-DESY - INDIA-DESY Collaboration (2020_Join2-INDIA-DESY) (2020_Join2-INDIA-DESY)
4. FS-Proposal: I-20210190 EC (I-20210190-EC) (I-20210190-EC)
5. FS-Proposal: I-20220893 (I-20220893) (I-20220893)

Experiment(s):

1. PETRA Beamline P10 (PETRA III)
2. DESY NanoLab: Microscopy

Appears in the scientific report 2026

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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