Crystallization of asymmetric diblock copolymers from microphase-separated melts
Abstract
Microphase separation in semicrystalline block copolymers can be driven by two forces: thermodynamic incompatibility between the blocks in the melt or crystallization of one or more blocks. The diblock copolymers investigated here are polyethylene- b -poly(3-methyl-1-butene), all containing ≈26 wt % ethylene, prepared by hydrogenating high-1,4-polybutadiene- b -high-3,4-polyisoprene. This block asymmetry leads to a hexagonally-packed cylindrical morphology when microphase separation is present in the melt. The molecular weights are varied to obtain differing degrees of incompatibility in the melt, ranging from a single-phase (disordered) melt to a strongly segregated melt. X-ray scattering and differential scanning calorimetry are used to investigate the morphology resulting from crystallization in these melts as a function of thermal history. Crystallization from strongly segregated melts is confined to the cylindrical microdomains and produces a morphology essentially independent of thermal history. In the most strongly segregated diblock crystallized at 10−20 °C/min, chain folding within these cylindrical microdomains is preferentially oriented with the chain axis tilted 18 ± 4° from normal to the cylinder axis. In contrast to strongly segregated melts, the morphology produced by crystallization from weakly segregated melts is highly dependent upon thermal history. Faster cooling kinetically confines crystallization to cylinders, while slower cooling results in complete disruption of the cylindrical melt mesophase upon crystallization, leading to a lamellar morphology with a larger domain spacing.
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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 [103]
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 [103]
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- Authors
- Quiram, D. J., Register, R. A., & Marchand, G. R.
- Affiliations
- Princeton University (US)
- Dow Chemical (United States) (US)
- ORCID
- Register, Richard A.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 1997-08-01
- Volume
- 30
- Issue
- 16
- Pages
- 4551-4558
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1993705458
- Cited by
- 178
- References
- 38
- Citations by year
- 2026: 2 · 2024: 2 · 2022: 2 · 2021: 3 · 2020: 5 · 2019: 5 · 2018: 2 · 2017: 7 · 2016: 6 · 2015: 6 · 2014: 6 · 2013: 7 · 2012: 9
- FWCI
- 7.24
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- 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, microphase separation, block copolymer crystallization, cylindrical microdomains, hexagonal morphology, thermal history, crystallization kinetics, lamellar morphology, domain spacing, semicrystalline block copolymers
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