Nucleation and Crystallization in Double Crystalline Poly(p-dioxanone)-b-poly(ε-caprolactone) Diblock Copolymers
Abstract
The crystallization behavior of three double crystalline diblock copolymers containing poly(ε-caprolactone) and poly( p -dioxanone) has been studied via differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray scattering (WAXS). Crystallization and melting temperatures and enthalpies are compared among copolymers and to those of the corresponding homopolymers. Only one crystallization exotherm was observed for the diblocks. DSC and WAXS indicated that during isothermal crystallization PPDX crystallized first, followed by PCL. POM revealed a transformation of crystalline morphologies at around 50 °C, from granular aggregates at high temperature (where only PPDX is crystalline) to banded spherulites at lower temperature, where both blocks were crystalline. The kinetics of crystallization were studied in detail via spherulite growth rates obtained from POM, and it was found that PPDX crystallization in the diblocks occurred much more slowly than in the homopolymers, this being responsible for the observed coincident crystallization of the two blocks during DSC cooling scans. On the other hand, the crystallized PPDX acts to nucleate the PCL block, so that heterogeneous crystallization was always observed even in copolymers containing a minority of this component (23%), for which “confined” crystallization might be expected. The crystallization kinetics of the PCL in the copolymers is accelerated by the presence of the crystalline PPDX block.
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Similar results where a crystallizable block is affected by a second rubbery block during isothermal crystallization have been reported for PPDX-b-PCL diblock copolymers.
“Similar results where a crystallizable block is affected by a second rubbery block during isothermal crystallization has been reported by some of us for PPDXb -PCL diblock copolymers. [7,12]”
The understanding of the complicated properties of double crystalline diblock copolymer systems is still at a nascent stage.
“Although there have been a number of prior reports on double crystalline diblock copolymer systems, the understanding of their complicated properties is still at a nascent stage. [5-16]”
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- Authors
- Albuerne, J., Márquez, L., Müller, A. J., Raquez, J. M., Degée, P., Dubois, P., Castelletto, V., & Hamley, I. W.
- Affiliations
- University of Leeds (GB)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2003-02-06
- Volume
- 36
- Issue
- 5
- Pages
- 1633-1644
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2067778928
- Cited by
- 174
- References
- 33
- Citations by year
- 2025: 2 · 2024: 1 · 2023: 1 · 2022: 2 · 2021: 4 · 2020: 5 · 2019: 6 · 2018: 4 · 2017: 10 · 2016: 8 · 2015: 9 · 2014: 15 · 2013: 10 · 2012: 12
- FWCI
- 12.36
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- PolyPublie (École Polytechnique de Montréal) (submittedVersion)
- 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 › Block Copolymer Self-Assembly
- Keywords
- poly(p-dioxanone), polycaprolactone, diblock copolymers, nucleation, crystallization kinetics, spherulite growth, heterogeneous crystallization, confined crystallization, crystallization exotherm, crystal morphology, crystallization enthalpy
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