Dynamics of Structure Formation and Crystallization in Asymmetric Diblock Copolymers
Abstract
The crystallization behavior of a series of ethylene- b -(3-methyl-1-butene) diblocks (E/MB) is investigated via simultaneous, time-resolved small-angle and wide-angle X-ray scattering. All the diblocks contain 26−27 wt % E, but possess varying molecular weights and hence varying segregation strengths in the melt, ranging from homogeneous to strongly segregated. Crystallization from homogeneous or weakly segregated melts at typical rates yields a semicrystalline solid consisting of alternating E and MB lamellae. By contrast, a strongly segregated diblock shows crystallization within the E cylinders that are present in the melt, even for slow crystallization rates and at temperatures where both blocks are well above their glass transition temperatures. Modest differences in intercylinder spacing between the melt at high temperatures and solid at low temperatures are shown to arise from the temperature dependence of the intercylinder spacing in the melt. Because chain diffusion in these block copolymer melts is not always fast on the crystallization time scale, the value of the melt spacing that is “frozen in” upon crystallization depends on the specimen’s thermal history. Despite the marked differences in the final structure between polymers where crystallization is constrained to cylinders and those where it “breaks out” to form lamellar microdomains, the kinetics are not remarkably different, at least in these polyethylene-based systems.
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In medium segregated systems (medium χN values, T_ODT > Tc > Tg), the final morphology depends on the applied thermal procedure: if the sample is cooled from the melt very fast (quenching), the morphology of the melt is maintained; otherwise, the final morphology is governed by the crystallization process.
“For these block copolymers the final morphology (i.e., the morphology of the solidified sample) depends on the applied thermal procedure: if the sample is cooled from the melt very fast, i.e., quenching, the morphology of the melt is maintained. Otherwise, the final morphology will be governed by the crystallization process [ 102 , 103 , 150-153 , 160-164 , 172 , 173 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [102]
In weakly segregated systems (low χN values, T_ODT > Tc > Tg), there is little morphological restriction for crystallization, allowing a break out from the ordered melt structure, so crystallization determines the final structure, usually forming crystalline lamellae and erasing the previous melt structure.
“In this case, there is little morphological restriction for the crystallization process, which allows a break out from the ordered melt structure, therefore the crystallization determines the final structure, usually crystalline lamellae are formed, erasing the previous structure of the melt [ 102 , 103 , 109 , 121 , 125 , 150-153 , 160-171 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [102]
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- Authors
- Quiram, D. J., Register, R. A., Marchand, G. R., & Ryan, A. J.
- Affiliations
- Princeton University (US)
- Dow Chemical (United States) (US)
- University of Manchester (GB)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 1997-12-01
- Volume
- 30
- Issue
- 26
- Pages
- 8338-8343
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2006432483
- Cited by
- 115
- References
- 21
- Citations by year
- 2026: 1 · 2025: 1 · 2024: 1 · 2022: 2 · 2021: 4 · 2020: 2 · 2019: 1 · 2017: 7 · 2016: 5 · 2015: 3 · 2014: 2 · 2013: 5 · 2012: 3
- FWCI
- 4.84
- 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
- asymmetric diblock copolymers, block copolymer crystallization, semicrystalline polymers, lamellar microdomains, chain diffusion, melt segregation, crystallization kinetics, microphase separation
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