Molecular dynamics of the asymmetric blend PVME/PS revisited by broadband dielectric and specific heat spectroscopy: Evidence of multiple glassy dynamics
- The molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding toThe molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding to the Kuhn segment length for the former relaxation and to the CRR for the latter one. The observed multiple glassy dynamics result from spatial local compositional heterogeneities on a microscopic level. Additionally, SHS investigations were performed for the first time for this system, proving an existence of a fourth relaxation process (α3-relaxation) due to the cooperative fluctuations of both PS and PVME segments. The separation between the thermal α3- and dielectric α2-relaxation increases dramatically with increasing polystyrene concentration, proving that the thermal response is dominated by PS.…
Autor*innen: | Paulina SzymoniakORCiD, Sherif Madkour, Andreas SchönhalsORCiD |
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Dokumenttyp: | Zeitschriftenartikel |
Veröffentlichungsform: | Verlagsliteratur |
Sprache: | Englisch |
Titel des übergeordneten Werkes (Englisch): | Macromolecules |
Jahr der Erstveröffentlichung: | 2019 |
Organisationseinheit der BAM: | 6 Materialchemie |
6 Materialchemie / 6.6 Physik und chemische Analytik der Polymere | |
Verlag: | ACS Publications |
Jahrgang/Band: | 52 |
Ausgabe/Heft: | 4 |
Erste Seite: | 1620 |
Letzte Seite: | 1631 |
DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten |
Freie Schlagwörter: | Broadband dielectric spectroscopy; Dynamic heterogeneity; Polymer blends; Specific heat spectroscopy |
Themenfelder/Aktivitätsfelder der BAM: | Material |
Material / Nano | |
DOI: | 10.1021/acs.macromol.8b02697 |
ISSN: | 0024-9297 |
Verfügbarkeit des Dokuments: | Datei im Netzwerk der BAM verfügbar ("Closed Access") |
Datum der Freischaltung: | 11.03.2019 |
Referierte Publikation: | Ja |
Datum der Eintragung als referierte Publikation: | 15.03.2019 |