Differences between isotropic and self-nucleated PCL melts detected by dielectric experiments
Abstract
Melt memory effects on polymer crystallization are commonly reported in the literature, even when they are not completely understood. In particular, the exact nature of the melt heterogeneities that cause an enhanced nucleation (i.e., the “self-nuclei”) is unknown. This is partly due to sensitivity limitations of the experimental techniques employed to study melt memory. In this work, the melt memory effect of semicrystalline polymers is studied for the first time by dielectric measurements. Polycaprolactones of two different molecular weights have been investigated. Isotropic or self-nucleated melt states are obtained, at a given experimental temperature, by cooling from the isotropic melt or heating from the semicrystalline solid, respectively. A detectable decrease in electrical permittivity is obtained for a self-nucleated melt, consistent with the presence of molecular dipoles with restricted mobility in the case of samples displaying crystalline memory. The volume fraction of repeating units involved in the formation of self-nuclei is estimated to be lower than 0.4%. The relative difference in dielectric permittivity between self-nucleated and isotropic melt state shows excellent correlation with rheological measurements that detect an increase in Newtonian viscosity and with the enhancement of nucleation density, measured by DSC. Each of these measured parameters showed a different sensitivity to the presence of self-nuclei, which is linked both to their nature and to the features of the specific measurements. It is suggested that the relatively strong memory effect displayed by PCL, which can be evidenced by different techniques, is related to the presence of weak intermolecular hydrogen-bonding interactions.
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Our group has proposed a division of Domain II into two sub-Domains.
“Our group has proposed a division of Domain II into two sub-Domains [333] .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [333]
It has been postulated that self-nuclei in Domain IIa can be regions in the melt where partial orientation of the chains remains, due to the survival of inter-segmental interactions that were present in the crystalline state.
“It has been postulated that they can be regions in the melt where partial orientation of the chains remain, thanks to the survival of inter-segmental interactions that were present in the crystalline state [ 321 , 322 , 333-337 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [333]
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Self-citation
- Authors
- Sangroniz, L., Alamo, R. G., Cavallo, D., Santamaría, A., Müller, A. J., & Alegría, A.
- Affiliations
- University of the Basque Country (ES)
- Florida A&M University - Florida State University College of Engineering (US)
- University of Genoa (IT)
- Ikerbasque (ES)
- Departamento de Física de Materiales, University of the Basque Country UPV/EHU and Centro de Física de Materiales (CFM) (CSIC-UPV/EHU) - Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain
- Corresponding author
- Müller, A. J.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-05-03
- Volume
- 51
- Issue
- 10
- Pages
- 3663-3671
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2802325613
- Cited by
- 81
- References
- 34
- Citations by year
- 2026: 8 · 2025: 12 · 2024: 9 · 2023: 12 · 2022: 16 · 2021: 6 · 2020: 11 · 2019: 6 · 2018: 1
- FWCI
- 3.00
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- DIGITAL.CSIC (Spanish National Research Council (CSIC)) (submittedVersion)
- CINECA IRIS Institutial Research Information System (University of Genoa) (submittedVersion)
- Funders
- Ministerio de Econom?a y Competitividad (MAT2014-53437-C2-P, MAT2017-83014-C2-1-P)
- Eusko Jaurlaritza (IT586-13)
- Division of Materials Research (DMR 1607786)
- Gobierno de Espa?a
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Keywords
- polycaprolactone, self-nucleation, polymer crystallization, dielectric constant, semicrystalline polymers, molecular dipoles, nucleation density, hydrogen bonding, isotropic melt, rheology, molecular weight effects
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