Crystallization of isotactic polypropylene under the spatial confinement templated by block copolymer microdomains
Abstract
We investigate the crystallization behavior of isotactic polypropylene (iPP) under the influence of nanoscale confinement templated by the microphase-separated structure of an iPP-based diblock copolymer system, isotactic polypropylene-block-atactic polystyrene (iPP-b-aPS). Three types of iPP microdomains, i.e., lamellae, cylinder, and sphere, were generated by controlling the composition of the diblock. The effect of microdomain morphology on the nucleation mechanism, crystallization kinetics, self-nucleation behavior, the population of the helical sequence of iPP block in the melt state, and crystal orientation have been systematically studied. It was found that the crystallization rate of iPP was predominantly controlled by homogeneous nucleation when the crystallization process was largely confined within the individual cylindrical and spherical microdomains. Such a nucleation mechanism and the highly frustrated crystal growth in the isolated microdomains led to the absence of Domain II and atypical crystallization kinetics in Domain III in the self-nucleation study. The population of the longer helical sequence of iPP block revealed by infrared spectroscopy was found to be affected by temperature but not by the spatial confinement, chain stretching, and junction point constraint imposed by the microdomains. Finally, the orientation of α-form iPP crystals in the lamellae-forming iPP-b-aPS was identified over a broad range of crystallization temperatures (T(c)). Different from other crystalline-amorphous diblocks, a lamellar branching of α-form iPP was observed in the lamellar microdomains at T(c) lying between 15 and 80 °C, where the daughter lamellae developed from the perpendicularly orientated parent iPP crystals with a specific angle of 80° or 100°. Once the sample was crystallized at T(c) ≤ 10 °C, the iPP crystals became randomly oriented.
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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 [101]
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- Authors
- Lin, M.-C., Chen, H.-L., Lin, W.-F., Huang, P.-S., & Tsai, J.-C.
- Affiliations
- National Tsing Hua University (TW)
- Department of Chemical Engineering, National Chung Cheng University, Chia-Yi 62142, Taiwan
- National Chung Cheng University (TW)
- Corresponding author
- Chen, Hsin-Lung
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-09-28
- Volume
- 116
- Issue
- 40
- Pages
- 12357-12371
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2328858329
- Cited by
- 27
- References
- 56
- Citations by year
- 2026: 1 · 2022: 2 · 2021: 2 · 2020: 2 · 2019: 5 · 2018: 6 · 2017: 4 · 2015: 4 · 2013: 1
- FWCI
- 1.26
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry B (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Council
- National Tsing Hua University
- National Chiao Tung University
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Materials Chemistry › Solidification and crystal growth phenomena
- Keywords
- isotactic polypropylene, polymer crystallization, spatial confinement, diblock copolymers, homogeneous nucleation, crystallization kinetics, self-nucleation, crystal orientation, lamellar microdomains
- MeSH terms
- Crystallization, Kinetics, Polypropylenes, Polystyrenes
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