Homogeneous nucleation and fractionated crystallization in block copolymers
Abstract
The confinement of crystallizable blocks within AB or ABC microphase-separated block copolymers in the nanoscopic scale can be tailored by adequate choice of composition, molecular weight, and chemical structure. In this work we have examined the crystallization behavior of a series of AB and ABC block copolymers incorporating one or two of the following crystallizable blocks: polyethylene, poly(ε-caprolactone), and poly(ethylene oxide). The density of confined microdomain structures (MD) within block copolymers of specific compositions, in cases where the MD are dispersed as spheres, cylinders, or any other isolated morphology, is much higher than the number of heterogeneities available in each crystallizable block. Therefore, fractionated crystallization takes place with one or several crystallization steps at decreasing temperatures. In specific cases, the clear observation of exclusive crystallization from homogeneous nuclei was obtained. The results show that, regardless of the specific morphological features of the MD, it is their vast number as compared to the number of heterogeneities present in the system that determines the fractionated character of the crystallization or in extreme cases homogeneous nucleation. The self-nucleation behavior was also found to depend on the composition of the copolymers. When the crystallizable block is confined into spheres or cylinders and exhibits homogeneous nucleation, the self-nucleation domain disappears. This is a direct consequence of the extremely high density of microdomain structures that need to be self-seeded (on the order of 10 15 −10 16 /cm 3 ). Therefore, to increase the density of self-nuclei, the self-nucleation temperature has to be decreased to values so low that extensive partial melting is achieved, and some of the unmelted crystal fragments can be annealed, in some cases even before self-nucleation takes place.
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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 [129]
The 20 °C crystallization peak of the unpurified PE-b-PEP-b-PEO sample was caused by Wilkinson catalyst, since it disappears in the purified sample; thus Wilkinson catalyst acts as a heterogeneous nucleating agent.
“This result indicates that the crystallization peak at 20 °C of the unpurified sample was caused by Wilkinson catalyst, since it disappears in the case of the purified sample [129] .Thus, Wilkinson catalyst acts as heterogeneous nucleating agent.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [129]
Impurities are able to act as heterogeneous nuclei.
“Impurities are able to act as heterogeneous nuclei, as has been proved by Müller et al. [129] .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as Müller et al. [129]
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- Authors
- Müller, A. J., Balsamo, V., Arnal, M. L., Jakob, T., Schmalz, H., & Abetz, V.
- Affiliations
- University of Bayreuth (DE)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-03-12
- Volume
- 35
- Issue
- 8
- Pages
- 3048-3058
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2063762360
- Cited by
- 226
- References
- 30
- Citations by year
- 2026: 8 · 2025: 6 · 2024: 3 · 2023: 2 · 2022: 8 · 2021: 11 · 2020: 11 · 2019: 5 · 2018: 3 · 2017: 10 · 2016: 7 · 2015: 11 · 2014: 11 · 2013: 13 · 2012: 13
- FWCI
- 14.10
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- ERef Bayreuth (University of Bayreuth) (submittedVersion)
- 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
- block copolymers, homogeneous nucleation, fractional crystallization, confined crystallization, microphase separation, polyethylene, polycaprolactone, poly(ethylene oxide), self-nucleation, crystal morphology, partial melting, annealing
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