Segmental Dynamics Govern the Cold Crystallization of Poly(lactic acid) in Nanoporous Alumina
Open accessAbstract
How segmental mobility influences the crystallization behavior of polymers in confined spaces is still not fully understood. In the present work, a systematic study of the segmental dynamics was carried out by dielectric relaxation spectroscopy (DRS) on racemic poly( dl -lactic acid) (PDLLA) confined in nanoporous alumina. The effects of the pore size and thermal history were examined. Two glass transition temperatures ( T g ) were observed, and an unusual “hysteresis” of the segmental relaxation time was detected. At lower temperatures, the segmental mobility of PDLLA “speeds up” first and “slows down” upon annealing. Both effects indicate the dynamically heterogeneous and nonequilibrium nature of chain segments under confinement. The “equilibrating process” of the relaxation time was monitored by DRS, and the characteristic time exhibited Arrhenius behavior. The experimental evidence supports a reversible adsorption/desorption mechanism of chain segments. The enhanced cold crystallization of poly(lactic acid) (PLLA) we reported previously ( Macromolecules, 2015, 48 (8), 2526–2533) can be explained adequately with the “enhanced mobility” of segments. This was further justified by the shift of the cold crystallization temperature toward higher temperatures of infiltrated PLLA after annealing.
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A highly mobile layer at the AAO/PLLA interface explains the higher nucleation rates, and its mobility depends strongly on adsorption during annealing, which affects the crystallization rate.
“A further study revealed that there was a highly mobile layer in the interface of AAO/PLLA which was used to explain the higher nucleation rates.The mobility of the interfacial layer depended strongly on the adsorption effect during annealing which in turn affected the crystallization rate [346] .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [346]
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- Authors
- Shi, G., Guan, Y., Liu, G., Müller, A. J., & Wang, D.
- Affiliations
- Chinese Academy of Sciences (CN)
- Ikerbasque (ES)
- Corresponding author
- Liu, Guoming
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-09-04
- Volume
- 52
- Issue
- 18
- Pages
- 6904-6912
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2971478594
- Cited by
- 48
- References
- 51
- Citations by year
- 2026: 7 · 2025: 5 · 2024: 7 · 2023: 7 · 2022: 5 · 2021: 12 · 2020: 5
- FWCI
- 2.35
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- Locations
- Macromolecules (publishedVersion)
- Communities in ADDI (Universidad del Pais Vasco) (submittedVersion, other-oa)
- LA Referencia (Red Federada de Repositorios Institucionales de Publicaciones Científicas) (submittedVersion)
- Hispana (submittedVersion, other-oa)
- Funders
- Ministry of Science and Technology of the People's Republic of China (2017YFE0117800)
- Ministerio de Econom?a y Competitividad (MAT2017-83014-C2-1-P)
- Youth Innovation Promotion Association of the Chinese Academy of Sciences (2015026)
- H2020 Marie Sklodowska-Curie Actions (H2020-MSCA-RISE-2017-778092)
- National Natural Science Foundation of China (21873109, 51820105005)
- State Key Laboratory of Polymer Physics and Chemistry (201510)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- polylactic acid, cold crystallization, segmental motion, segmental mobility, nanoporous alumina, confined polymers, dielectric relaxation, glass transition temperature, pore size effects, thermal history, annealing, adsorption-desorption, polymer crystallization
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
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