Effect from Miktoarm Star-Like Chain Architectures on Nonequilibrium Self-Assembly of Block Copolymers

doi:10.19894/j.issn.1000-0518.250113

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (8): 1087-1095.DOI: 10.19894/j.issn.1000-0518.250113

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Effect from Miktoarm Star-Like Chain Architectures on Nonequilibrium Self-Assembly of Block Copolymers

Xiao YANG¹^,², De-Wen SUN¹^,²()

^1.State Key Laboratory of Polymer Science and Technology，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China

Received:2025-03-17 Accepted:2025-06-04 Published:2025-08-01 Online:2025-08-11
Contact: De-Wen SUN
About author:dwsun@ciac.ac.cn
Supported by:
the Science and Technology Development Program of Jilin Province(20240101173JC);the National Natural Science Foundation of China(21973090)

Abstract

Abstract:

Block copolymers have the ability to form a variety of ordered mesostructures at the length scale of nanometers via spontaneous self-assembly. These ordered nanostructures have significant potential applications in many fields， e.g.， battery electrode materials， advanced semiconductor devices， three-dimensional （3D） photonic crystals， etc.， and therefore， they have attracted great attention in the field of high-performance material science. With the development of polymer synthesis technology， more and more chain architectures have been synthesized， such as miktoarm star-like chain architectures. Whereas the effect from the chain architectures on the equilibrium self-assembly of block copolymers is well known to researchers and has been widely employed to stabilize the desired ordered mesostructures of block copolymers， the influence of the chain architectures on the nonequilibrium self-assembly of block copolymers is currently rarely considered. In this work， based on the thermodynamically stable hex mesophase in miktoarm star-like AB _m block copolymers， by designing miktoarm star-like A（CB） _m block copolymers， where the chemophysical properties of C-blocks can be rapidly altered from B to A， to generate unstable states， we explore the nonequilibrium self-assembly ensuing from these unstable states as well as the effect from the number of C-blocks， i.e.， the value of m， and the chain length of each C-block. Our obtained results show that the more the value of m， the smaller the volume-fraction interval that is available for the nonequilibrium self-assembly ensuing from the generated unstable states to reach ordered mesostructures. For 2≤m≤4， in addition to hex， the ordered cylindrical mesostructure with graphene-like arrangement of cylinders also can be reached by the nonequilibrium self-assembly ensuing from the generated unstable states， however， when m=5， the ordered mesostructure that can be reached by the nonequilibrium self-assembly ensuing from the generated unstable states is only hex.

Key words: Block copolymer, Chain architecture, Nonequilibrium self-assembly, Rapid-component change, Cylindrical mesostructure

CLC Number:

O631

Xiao YANG, De-Wen SUN. Effect from Miktoarm Star-Like Chain Architectures on Nonequilibrium Self-Assembly of Block Copolymers[J]. Chinese Journal of Applied Chemistry, 2025, 42(8): 1087-1095.

Figures/Tables 4

Fig.1 Miktoarm star-like A（B′B） m block copolymers before rapid-component change （left part） and miktoarm star-like A（A′B） m block copolymers after rapid-component change （right part）

Fig.2 The effect from the size L， on the free energies of thermodynamically stable hexagonally packed cylinders in miktoarm star-like AB m block copolymers， where 2≤m≤5

Fig.3 The diagram of states reached by the nonequilibrium self-assembly starting from the generated unstable states， where the red dashed-dotted line indicates the volume fraction fA=0.4 of A-block before the rapid component change

Fig.4 The nonequilibrium kinetics of structural formation of hexB when m=2 and fA*=0.682 after the rapid-component change. The blue color represents the component B， whereas the green color represents the interface between components A and B

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Effect from Miktoarm Star-Like Chain Architectures on Nonequilibrium Self-Assembly of Block Copolymers

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