writer：Nan Yan, Yutian Zhu, Wei Jiang
keywords：AB两嵌段共聚物, 软纳米液滴, 三维软受限, Monte Carlo模拟, 自组装, 形貌转变
source：期刊
specific source：The Journal of Physical Chemistry B, 2016, 120(46), 12023-12029
Issue time：2016年

摘要：通过Monte Carlo模拟与实验相结合，研究了AB型两嵌段共聚物在三维软纳米液滴中的自组装行为，系统考察了受限程度和每个嵌段与边界界面的界面相互作用这两个关键因素对三维软受限自组装的影响。模拟结果表明，随着受限程度（以D/L比衡量，L为聚合物链长，D为最终聚合物粒子的约化直径）增强，嵌段共聚物链越来越折叠，引发一系列形貌转变。基于模拟预测，在乳液液滴内对对称和不对称嵌段共聚物进行三维受限自组装实验，实验结果很好地重现了模拟预测的受限程度诱导形貌转变，例如从分段蛹状粒子到汉堡粒子的转变，以及从覆盆子状粒子到三角状粒子再到汉堡粒子的转变。该研究表明，三维软受限下的自组装纳米结构可通过调节受限程度和界面性质，即D/L比及每个嵌段与边界界面的相互作用，简单调控。

Abstract：The self-assembly of AB-type diblock copolymers confined in a three-dimensional (3D) soft nanodroplet is investigated by the combination of Monte Carlo simulation and experiment. The influences of two critical factors, i.e., confinement degree of the imposed confinement space and the interfacial interaction between each individual block and boundary interface, on the 3D soft confined self-assembly are examined systematically. The simulation results reveal that block copolymer chains become more and more folded as the confinement degree (monitored by the ratio of D/L) is enhanced, causing a series of morphological transitions. Based on the simulation prediction, corresponding experiments are performed by the 3D confined self-assembly of both symmetric and asymmetric block copolymers within emulsion droplets. The experimental results well reproduce the confinement degree induced morphological transitions predicted by the simulations, such as the transition from segmented pupa-like particle to hamburger particle and the transition from raspberry-like particle to triangle-like particle, and then to hamburger particle. The current study implies that self-assembled nanostructures under 3D soft confinement can be simply controlled by tuning the confinement degree and interfacial property.

论文链接：https://doi.org/10.1021/acs.jpcb.6b10170