Cited by 74Material Dynamics and PropertiesPolymer crystallization and propertiesRheology and Fluid Dynamics Studies

Molecular-weight dependence of enthalpy relaxation of PMMA

Andreozzi, Laura, Faetti, Massimo, Giordano, Marco, Zulli, Fabio·2005·Macromolecules

Abstract

The effects of the molecular weight on the physical aging of polymers were investigated by means of differential scanning calorimetry (DSC) experiments in five PMMA samples with mass values across the entanglement mass M e . The Tool−Narayanaswamy−Moynihan (TNM) model and a recent configurational entropy approach were systematically compared with the experiments. For the samples with the lowest molecular weights, the two approaches exhibited similar agreement with experiments; however, in the systems with higher molecular weights, the TNM model met major difficulties, and a clear improvement was obtained with the other model. The additional parameter introduced by the entropic model showed a strong molecular-weight dependence, with a sharp increase at the entanglements mass of PMMA. These results evidence the role of the chain entanglements on the physical aging of polymers. Finally, the influence of the molecular weight on the fragility was investigated and related to the recent literature debates on this topic.

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Crossref · 10.1021/ma0507037

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Authors
Andreozzi, L., Faetti, M., Giordano, M., & Zulli, F.
Affiliations
University of Pisa (IT)
Corresponding author
Andreozzi, Laura
Venue
Macromolecules
Published
2005-06-18
Volume
38
Issue
14
Pages
6056-6067
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
OpenAlex
W1966147004
Cited by
74
References
53
Citations by year
2026: 3 · 2025: 3 · 2024: 7 · 2023: 2 · 2022: 5 · 2021: 2 · 2020: 6 · 2019: 3 · 2018: 1 · 2017: 4 · 2016: 4 · 2015: 3 · 2014: 3 · 2013: 5 · 2012: 2
FWCI
2.64
Type
journal article
Language
en
Open access
closed
Locations
  • Macromolecules (publishedVersion)
  • CINECA IRIS Institutial research information system (University of Pisa) (submittedVersion)
Topics
  • Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
  • Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Rheology and Fluid Dynamics Studies
Keywords
PMMA, physical aging, enthalpy relaxation, molecular weight dependence, Tool-Narayanaswamy-Moynihan model, configurational entropy, chain entanglement, fragility, polymer relaxation

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