Multiple nucleation events and local dynamics of poly(ε-caprolactone) (PCL) confined to nanoporous alumina
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The crystallization and local dynamics of poly(ε-caprolactone) (PCL) confined to self-ordered nanoporous alumina (AAO) were studied as a function of pore size, pore surface functionality, molecular weight and cooling/heating rate by differential scanning calorimetry (DSC), wide-angle X-ray diffraction and dielectric spectroscopy. In contrast to the bulk, PCL located inside nanoporous alumina crystallizes via several distinct nucleation mechanisms. All mechanisms display pronounced rate dependence. At low undercoolings, the usual heterogeneous nucleation of bulk PCL was suppressed at the expense of two additional mechanisms attributed to heterogeneous nucleation initiated at the pore walls. At higher undercoolings a broad peak was observed in DSC which we attribute to crystallization initiated by homogeneous nucleation. At high cooling rates, the critical nucleus size is smaller than the smallest diameter of pores. Thus, PCL is able to crystallize within the smallest pores, despite the lower degree of crystallinity. Inevitably, homogeneous nucleation is strongly coupled to the local viscosity and hence to the local segmental dynamics. Dielectric spectroscopy revealed that confinement affected both the rate of segmental motion with a lowering of the glass temperature as well as a broader distribution of relaxation times.
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By controlling the surface cleaning procedure and producing a partial cleaning, similar fractionated crystallization behavior of the same polymer in previous studies can be reproduced.
“By controlling the surface cleaning procedure, and producing a”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
The Experimental section (page unavailable) says excess PCL was removed from the alumina surface, and the Conclusion reports several crystallization mechanisms for confined PCL. Neither passage says the authors varied the cleaning procedure, performed partial cleaning, or reproduced fractionated crystallization behavior from previous studies. (LLM, conf=0.72)
Experimental — accuracy not yet measuredBulk PCL shows a single crystallization temperature at 32 °C.
“the bulk PCL shows a single T c at 32 °C (peak A).”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
Two or three exothermic peaks were observed for infiltrated PCL samples.
“Two or three exothermic peaks (Peak B, C and D) were observed for the infiltrated PCL samples.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
The other PCL peaks were interpreted as heterogeneous nucleation of a different kind compared with bulk, because the number of pores is several orders of magnitude larger than the density of heterogeneities in the sample.
“The other peaks were interpreted as originating from”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
The lowest exothermic peak for infiltrated PCL was assigned to homogeneous nucleation.
“Similarly, the lowest exothermic peak (peak E) was assigned to homogeneous nucleation.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
It was hypothesized that the unusual heterogeneous nucleation in PCL/AAO was initiated from the pore walls.
“It was hypothesized that the unusual heterogeneous nucleation was initiated from the pore walls.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [271]
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- Authors
- Suzuki, Y., Duran, H., Akram, W., Steinhart, M., Floudas, G., & Butt, H.-J.
- Affiliations
- Max Planck Society (DE)
- Osnabrück University (DE)
- University of Ioannina (GR)
- Corresponding author
- Floudas, George
- Venue
- Soft Matter
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2013
- Volume
- 9
- Issue
- 38
- Pages
- 9189
- ISSN
- 1744-683X (ISSN-L)
- 1744-6848
- OpenAlex
- W2128166891
- Cited by
- 118
- References
- 38
- Citations by year
- 2026: 3 · 2025: 6 · 2024: 1 · 2023: 8 · 2022: 4 · 2021: 11 · 2020: 11 · 2019: 10 · 2018: 13 · 2017: 19 · 2016: 15 · 2015: 12 · 2014: 4
- FWCI
- 7.46
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- cc-by
- Locations
- Soft Matter (publishedVersion, cc-by)
- Funders
- European Commission (2007–2013)
- Deutscher Akademischer Austauschdienst
- Deutsche Forschungsgemeinschaft (BU 1556/31-1, SPP1369, STE 1127/13, INST 190/134-1)
- Max-Planck-Institut für Polymerforschung
- 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, nanoporous alumina, polymer crystallization, nucleation mechanism, heterogeneous nucleation, homogeneous nucleation, pore size effects, cooling rate dependence, segmental motion, glass transition, distribution of relaxation times, polymer confinement
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