Chain orientation in block copolymers exhibiting cylindrically confined crystallization
Abstract
The orientation of the crystal stems in diblock copolymers, where crystallization occurs within the cylindrical microdomains present in the melt mesophase, is investigated via X-ray scattering on flow-aligned specimens. A series of ethylene-b-(3-methyl-1-butene) diblocks (E/MB) is compared with an ethylene-b-(vinylcyclohexane) diblock (E/VCH), where MB is rubbery (Tg < Troom) and VCH is vitreous (Tg = 134 degreesC) at the freezing point of the E block. All of the diblocks contain 26-28 wt % E, leading to a morphology of hexagonally-packed E cylinders. Crystallization in all of these materials can be confined to the cylindrical microdomains. Not only do the crystals align preferentially within the semicrystalline cylinders, but this orientation varies depending on the ability of chains to diffuse during the crystallization process. When chain diffusion is most rapid, alignment is observed with the chain axis in the crystals perpendicular to the cylinder axis and the b axis (fast growth axis) coincident with the cylinder axis. However, when the chain mobility is limited, the crystal stems tilt with respect to a plane which is normal to the cylinder axis, allowing better accommodation of amorphous material at the crystallite surface.
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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 [104]
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- Authors
- Quiram, D. J., Register, R. A., Marchand, G. R., & Adamson, D. H.
- Affiliations
- Princeton University (US)
- Dow Chemical (United States) (US)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 1998-07-01
- Volume
- 31
- Issue
- 15
- Pages
- 4891-4898
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2010631577
- Cited by
- 168
- References
- 30
- Citations by year
- 2025: 1 · 2024: 4 · 2023: 1 · 2022: 5 · 2021: 4 · 2020: 2 · 2019: 2 · 2018: 3 · 2017: 7 · 2016: 4 · 2015: 7 · 2014: 4 · 2013: 4 · 2012: 10
- FWCI
- 8.81
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- PubMed (publishedVersion)
- APS
- 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
- block copolymers, chain orientation, confined crystallization, cylindrical microdomains, diblock copolymers, flow alignment, chain diffusion, crystal tilt, semicrystalline polymers
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