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Emergence and Stability of Janus-Like Superstructures in an ABCA Linear Tetrablock Copolymer
Macromolecules ( IF 5.1 ) Pub Date : 2020-08-20 , DOI: 10.1021/acs.macromol.0c01328 Qiong Xie 1 , Yicheng Qiang 1 , Guojie Zhang 2 , Weihua Li 1
Macromolecules ( IF 5.1 ) Pub Date : 2020-08-20 , DOI: 10.1021/acs.macromol.0c01328 Qiong Xie 1 , Yicheng Qiang 1 , Guojie Zhang 2 , Weihua Li 1
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Although the general mechanism of block copolymer self-assembly has been well established, the self-assembly behaviors of multiblock copolymers are still hard to understand and are even quite counterintuitive. Herein, we investigate the self-assembly of a relatively simple multiblock copolymer, i.e., a symmetric ABCA linear tetrablock copolymer composed of equal B and C blocks as well as equal two end A blocks, focusing on the emergence and stability of Janus-like superspherical (JS) and supercylindrical (JC) morphologies. Intuitively, the JS and JC superstructures could be formed by this ABCA copolymer with proper compositions. Our study of self-consistent field theory shows that the JS morphology is formed in a certain range of 
(χ = χAB = χAC), e.g., 1.25 ≲ γ ≲ 2.25 for χN = 80. Surprisingly, the JS phase is located between the simple spherical phase and the disordered phase along the increasing γ. Moreover, a helical-Janus spherical (HS) phase is predicted to compete with the Janus-like spherical phase. Our results indicate that the JS phase has a higher B/C interfacial energy but a lower entropic contribution than the HS phase, which is quite counterintuitive. Whereas the Janus-like supercylinder is not predicted as stable, stable supercylinders composed of B/C helices (HC) and B/C stacked disks (CB/C) are predicted.
中文翻译：
ABCA线性四嵌段共聚物中Janus-Like上层结构的出现和稳定性
尽管已经很好地了解了嵌段共聚物自组装的一般机理，但是多嵌段共聚物的自组装行为仍然难以理解，甚至是违反直觉的。在本文中，我们研究了相对简单的多嵌段共聚物（即由相等的B和C嵌段以及相等的两个末端A嵌段组成的对称ABCA线性四嵌段共聚物）的自组装，重点研究了Janus状超球形聚合物的出现和稳定性。 （JS）和超圆柱（JC）形态。凭直觉，这种具有适当组成的ABCA共聚物可以形成JS和JC超结构。该JS形态在一定范围内的形成提供了自洽场理论表明研究（χ=χ AB =χ AC），例如，1.25≲γ≲2.25χ Ñ = 80。令人惊讶地，相JS位于简单球形相位和沿增加γ无序相之间。此外，螺旋-Janus球形（HS）相预计将与Janus样球形相竞争。我们的结果表明，与HS相相比，JS相具有更高的B / C界面能，但熵贡献却较低，这与直觉相当。尽管不能预测Janus形超缸是稳定的，但可以预测到由B / C螺旋（HC）和B / C堆叠盘（C B / C）组成的稳定超缸。
更新日期：2020-09-09
(χ = χAB = χAC), e.g., 1.25 ≲ γ ≲ 2.25 for χN = 80. Surprisingly, the JS phase is located between the simple spherical phase and the disordered phase along the increasing γ. Moreover, a helical-Janus spherical (HS) phase is predicted to compete with the Janus-like spherical phase. Our results indicate that the JS phase has a higher B/C interfacial energy but a lower entropic contribution than the HS phase, which is quite counterintuitive. Whereas the Janus-like supercylinder is not predicted as stable, stable supercylinders composed of B/C helices (HC) and B/C stacked disks (CB/C) are predicted.
中文翻译：
ABCA线性四嵌段共聚物中Janus-Like上层结构的出现和稳定性
尽管已经很好地了解了嵌段共聚物自组装的一般机理，但是多嵌段共聚物的自组装行为仍然难以理解，甚至是违反直觉的。在本文中，我们研究了相对简单的多嵌段共聚物（即由相等的B和C嵌段以及相等的两个末端A嵌段组成的对称ABCA线性四嵌段共聚物）的自组装，重点研究了Janus状超球形聚合物的出现和稳定性。 （JS）和超圆柱（JC）形态。凭直觉，这种具有适当组成的ABCA共聚物可以形成JS和JC超结构。该JS形态在一定范围内的形成提供了自洽场理论表明研究
（χ=χ AB =χ AC），例如，1.25≲γ≲2.25χ Ñ = 80。令人惊讶地，相JS位于简单球形相位和沿增加γ无序相之间。此外，螺旋-Janus球形（HS）相预计将与Janus样球形相竞争。我们的结果表明，与HS相相比，JS相具有更高的B / C界面能，但熵贡献却较低，这与直觉相当。尽管不能预测Janus形超缸是稳定的，但可以预测到由B / C螺旋（HC）和B / C堆叠盘（C B / C）组成的稳定超缸。
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