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The Decisive Role of Confinement in Enhancing or Suppressing Self‐Nucleation in Polyethylene‐Containing Block Copolymers

Titelangaben

Liao, Yilong ; Sangroniz, Leire ; Safari, Maryam ; Schmalz, Holger ; Müller, Alejandro:
The Decisive Role of Confinement in Enhancing or Suppressing Self‐Nucleation in Polyethylene‐Containing Block Copolymers.
In: Macromolecular Chemistry and Physics. (2025) . - e00056.
ISSN 1521-3935
DOI: https://doi.org/10.1002/macp.202500056

Abstract

The influence of confinement on the self-nucleation behavior of crystallizable polyethylene (PE) and poly(ethylene oxide) (PEO) blocks in block copolymers of different architectures was studied by differential scanning calorimetry. The amorphous blocks, polystyrene (PS) and poly(methyl methacrylate) (PMMA), with high glass transition temperatures, create glassy matrices that confine crystallization in the microphase-segregated block copolymers. For diblock copolymers (PS-b-PE, PMMA-b-PE), the PE blocks exhibit stronger melt memory than neat PE, as moderate confinement favors the preservation of the conformations adopted in the crystalline regions. However, when both ends of the PE block are tethered to glassy blocks, in PS-b-PE-b-PS and PS-b-PE-b-PMMA, melt memory and self-nucleation completely vanish as the confinement degree increases. In PS-b-PE-b-PEO triblock terpolymers, the self-nucleation of the PE block is hindered even at very low temperatures, where annealing is dominant. The PEO block undergoes a complex fractionated crystallization where self-nucleation disappears in the isolated, highly confined microdomains. SSA (successive self-nucleation and annealing) thermal fractionation results are similar for PE and PE blocks (i.e., hydrogenated polybutadiene), resulting from molecular defects caused by branching. Our results indicate that the melt memory of confined crystallizable blocks can be triggered by moderate confinement but completely suppressed when confinement is too strong.

Weitere Angaben

Publikationsform: Artikel in einer Zeitschrift
Begutachteter Beitrag: Ja
Keywords: Crystallizable blocks; confinement; block copolymers; self-nucleation; thermal fractionation
Institutionen der Universität: Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Makromolekulare Chemie II
Profilfelder > Advanced Fields > Polymer- und Kolloidforschung
Forschungseinrichtungen > Institute in Verbindung mit der Universität > Bayerisches Polymerinstitut (BPI)
Titel an der UBT entstanden: Ja
Themengebiete aus DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Eingestellt am: 03 Jun 2025 10:19
Letzte Änderung: 03 Jun 2025 10:19
URI: https://eref.uni-bayreuth.de/id/eprint/93882