Polymer crystallization confined in one, two or three dimensions
Abstract
We examine the crystallization behavior of polyethylene- b -poly(vinylcyclohexane) diblock copolymers, E/VCH, using a combination of transmission electron microscopy (TEM), dilatometry, and time-resolved small-angle X-ray scattering (SAXS). The glassy VCH matrix effectively restricts E crystallization to within the spheres, cylinders, gyroid channels, or lamellae formed by microphase separation in the melt. The VCH matrix can contract in response to crystallization of the E microdomains, so crystallization proceeds without cavitation. The crystallization kinetics strongly reflect the connectivity of the E microdomains: homogeneous nucleation and first-order crystallization kinetics for spheres or cylinders of E; conventional sigmoidal kinetics for the highly interconnected gyroid structure. Lamellar materials show an interesting two-step crystallization behavior: at higher temperature, heterogeneous nucleation permits the crystallization of lamellae interconnected through grain boundaries or defects, and then at lower temperature homogeneous nucleation permits the crystallization of the remaining isolated lamellae.
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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 [105]
In PE-b-PVCH copolymers studied by Loo et al., varying the ethylene-vinylcyclohexane composition allowed obtaining a wide range of morphologies: spheres, cylinders, gyroids or lamellae.
“Varying the ethylene-vinylcyclohexane composition, they were able to obtain a wide range of morphologies: spheres, cylinders, gyroids or lamellae.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [105]
In PE-b-PVCH copolymers, the melt morphology is preserved after the crystallization of the PE block.
“Analysing the data obtained at room temperature and at 160 °C, the authors concluded that the melt morphology is preserved after the crystallization of PE block, since the data corresponding to room temperature show one peak at low q values that corresponds to the melt morphology and additional higher order peaks appear for the different copolymers studied.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [105]
The number of microdomains in E/VCH 5/22 (spheres) is 9 × 10^16 microdomains per cm3 and in E/VCH 6/25 (cylinders) is 2 × 10^15 microdomains per cm3.
“The number of MDs in the E/VCH 5/22 sample, which forms spheres, is 9 × 10 16 microdomains per cm 3 and 2 × 10 15 microdomains per cm 3 in the case of E/VCH 6/25, in which cylinders are formed.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [105]
According to Loo et al., hydrogenated polybutadiene (precursor for the block copolymers) contains approximately 10^9 impurities per cm3.
“According to the estimations of Loo et al., hydrogenated polybutadiene (precursor for the block copolymers) contains approximately 10 9 impurities per cm 3 .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [105]
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- Authors
- Loo, Y.-L., Register, R. A., Ryan, A. J., & Dee, G. T.
- Affiliations
- Princeton University (US)
- University of Sheffield (GB)
- DuPont (United States) (US)
- Corresponding author
- Register, Richard A.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2001-11-01
- Volume
- 34
- Issue
- 26
- Pages
- 8968-8977
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1996328865
- Cited by
- 324
- References
- 32
- Citations by year
- 2026: 4 · 2025: 5 · 2024: 8 · 2023: 4 · 2022: 6 · 2021: 5 · 2020: 10 · 2019: 8 · 2018: 10 · 2017: 24 · 2016: 11 · 2015: 13 · 2014: 15 · 2013: 17 · 2012: 23
- FWCI
- 16.83
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Funders
- Division of Materials Research
- 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
- polymer crystallization, diblock copolymers, microphase separation, lamellae, crystallization kinetics, heterogeneous nucleation, homogeneous nucleation, two-step crystallization, confined crystallization, matrix contraction, time-resolved small-angle X-ray scattering
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