Molecular-weight dependence of enthalpy relaxation of PMMA
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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Lower molecular weight reduces the activation energy and accelerates both enthalpy relaxation and crystallisation.
“The activation energy for structural relaxation is also dependent on the molecular weight of a polymer, with a lower molecular weight known to reduce the activation energy and accelerate both enthalpy relaxation and crystallisation [17, 49, 50].”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [50]
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“and crystallisation [17, 49, 50].”
- Authors
- Andreozzi, L., Faetti, M., Giordano, M., & Zulli, F.
- Affiliations
- University of Pisa (IT)
- Corresponding author
- Andreozzi, Laura
- ORCID
- Andreozzi, Laura
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- 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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