Fractionated Crystallization and Fractionated Melting of Confined PEO Microdomains in PB-b-PEO and PE-b-PEO Diblock Copolymers
Abstract
The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene- b -poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene- b -poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB- b -PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder−sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.
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In strongly segregated systems (high χN values, T_ODT > Tg > Tc), the phase segregated structure of the melt is preserved, but the amorphous block is in the glassy state, so crystallization of the crystalline block occurs under hard confinement.
“The phase segregated structure of the melt is preserved, but in this case, the amorphous block is in the glassy state, therefore the crystallization process of the crystalline block occurs under hard confinement (the same behaviour is observed for double crystalline diblock copolymers, once the first block crystallizes, the second one crystallizes under hard confinement) [ 101 , 104 , 105 , 108 ,”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [128]
Similar low crystallization temperatures were also found in PEO confined within block copolymers or AAO templates.
“Similar low crystallization temperatures were also found in PEO confined within block copolymers or AAO templates (see previous sections) [ 128 , 218 , 277-280 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [128]
Low n values with first-order kinetics, other than in PEO/SiO2 and HDPE/CNT, were also observed in polymer droplets, AAO templates, and spherical microdomains of block copolymers.
“such low n values with a first-order kinetics, other than in PEO/SiO 2 and HDPE/CNT, were also observed in systems such as polymer droplets [315] , AAO templates [277] , and spherical microdomains of block copolymers [128] .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [128]
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- Authors
- Castillo, R. V., Arnal, M. L., Müller, A. J., Hamley, I. W., Castelletto, V., Schmalz, H., & Abetz, V.
- Affiliations
- University of Bayreuth (DE)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2008-01-03
- Volume
- 41
- Issue
- 3
- Pages
- 879-889
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2014843412
- Cited by
- 96
- References
- 33
- Citations by year
- 2026: 3 · 2025: 4 · 2024: 1 · 2023: 2 · 2022: 1 · 2021: 4 · 2020: 3 · 2019: 4 · 2018: 1 · 2017: 9 · 2016: 7 · 2015: 10 · 2014: 6 · 2013: 9 · 2012: 10
- FWCI
- 6.35
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- poly(ethylene oxide), diblock copolymers, confined crystallization, fractional crystallization, microdomains, spherical morphology, hydrogenation, nucleation, Avrami exponent, isothermal crystallization
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