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
- Particle Distribution Informed by Chain Rigidity in Diblock Copolymer Melts: The Effect of Entropy
- 高分子科学（英文版） 2024年42卷第3期页码：388-399
- Affiliations：
  
  School of Chemistry, Beihang University, Beijing 100191, China
- Author bio：
  
  qishuanhu@buaa.edu.cn (S.Q.)
  yjiang@buaa.edu.cn (Y.J.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 22173002). S.Q. acknowledges the Fundamental Research Funds for the Central Universities (No. YWF-22-K-101). J.Y. acknowledges the Fundamental Research Funds for the Central Universities from Beihang University. The SCF calculations were carried out on the high performance computer cluster at Beihang University.
- DOI：10.1007/s10118-023-3053-9
  中图分类号：
- 收稿：2023-09-09，
  
  修回：2023-9-18，
  
  录用：2023-9-20，
  
  网络首发：2023-11-03，
  
  纸质出版：2024-03-01
- Accepted：
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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, 2024, 42(3): 388-399.
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, 2024, 42(3): 388-399. 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.

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