Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy

Yuguo Chen; Shuanhu Qi; Ying Jiang

doi:10.1007/s10118-023-3053-9

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Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy

RESEARCH ARTICLE | Updated：2024-02-20

- Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy
  Enhanced Publication
- Chinese Journal of Polymer Science Vol. 42, Issue 3, Pages: 388-399(2024)
- Affiliations：
  
  School of Chemistry, Beihang University, Beijing 100191, China
- Author bio：
  
  qishuanhu@buaa.edu.cn (S.Q.)
  yjiang@buaa.edu.cn (Y.J.)
- Funds：
- DOI：10.1007/s10118-023-3053-9
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Chen, Y.; Qi, S.; Jiang, Y. Particle distribution informed by chain rigidity in diblock copolymer melts: the effect of entropy. Chinese J. Polym. Sci. 2024, 42, 388–399

Yuguo Chen, Shuanhu Qi, Ying Jiang. Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy. [J]. Chinese Journal of Polymer Science 42(3):388-399(2024)
Chen, Y.; Qi, S.; Jiang, Y. Particle distribution informed by chain rigidity in diblock copolymer melts: the effect of entropy. Chinese J. Polym. Sci. 2024, 42, 388–399 DOI： 10.1007/s10118-023-3053-9.

Yuguo Chen, Shuanhu Qi, Ying Jiang. Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy. [J]. Chinese Journal of Polymer Science 42(3):388-399(2024) DOI： 10.1007/s10118-023-3053-9.

摘要

Moderately semiflexible chains result in a local minimum free energy at the domain center of the lamellar microphase, which demonstrates the ability of tuning of the particle distribution in polymer microphases by chain flexibility.

Abstract

We study the effect of chain rigidity on tailoring the nanoparticle locations for neutral and selective particles embedded in the lamellar morphology formed by semiflexible diblock copolymer chains using self-consistent field calculations. The nanoparticles are modeled through a cavity function, and the semiflexible chains are represented by the continuous Kratsky-Porod chain model. In general situation, the nanoparticles prefer to stay at the interface in order to reduce the interface areas and thus the system free energy. However, the particle distribution at the domain center is subtle, and the underlying physics is intrinsically different depending on the polymer flexibility. In the case of flexible chains, the entropy just contributes a constant shift to the free energy when the nanoparticles move around the domain center indicating that the local metastable state if appears at the domain center is wholly attributed to the local minimum in the enthalpy. If the polymers are rigid, the variation of the particle distribution at the domain center has a close relation with the polymer rigidity and nanoparticle size. In the case of strongly rigid polymers with small nanoparticles, a nearly uniform particle distribution at the domain center is observed, while in other cases, a local enhancement of particle distribution there is found. In contrast to the case of flexible chains, further analysis reveals the crucial role of entropy in controlling the shape of particle distributions at the phase domain. Specifically, the local metastable state appears in the domain center is determined by the large entropy there which arises from the weak coupling of bond orientations that allows the polymer chains to be relatively relaxed. When the particle becomes selective, its distribution in the phase domain exhibits a shift almost uniformly rather than changes its profile, and the underlying physics still holds. In all, our study establishes a strong coupling between the chain rigidity and effect of entropy.

关键词

Keywords

Semiflexible diblock copolymerNanoparticle distributionSelf-consistent field theoryEntropic effect

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