聚合物/纳米颗粒嵌段体自组装行为及其有序结构的研究

Block copolymers have many phase structures and the self-assembly characteristics, and the nanoparticles have some unique optic, electric, magnetic and catalysis properties, therefore, copolymer/nanoparticles systems have more complicated structures and good properties, and the more applications can be paid. In this project, the self-assembly of diblock copolymers/diblock nanorods are investigated by using simulation method and self-consistent field theory (SCFT) and density functional theory (DFT). The orientation of nanorods and their spatial dispositions are explored, and the directed and collaborative self-assemblies are discussed. The phase separation and quasicrystal structures of nanorods/nanoparticles mixture systems induced by polymer brushes are also investigated by molecular dynamics simulation, and the fact that the entropy plays an important role on the phase separation can be well understood. The aggregation process and the quasicrystal structures of polymers/block nanoparticles mixture systems under the confinement conditions can also be studied by using simulation method, and the effects of the size and the shape of block nanoparticles on the quasicrystal structures are also discussed. The structures and its dynamical process of polymers/block nanoparticles mixtures under shear are also investigated using simulation methods and the effects of shear field and diblock nanorods on the structures can also be known. This project can provide some insights into the self-assembly processes and the ordered structures of complicated polymers/nanoparticles systems.

嵌段聚合物具有丰富相结构和自组装特征，纳米颗粒则具有独特的光、电、磁性质以及催化作用，所以聚合物/纳米颗粒体系具有更复杂结构与优越性能，因而具备良好的应用前景，备受人们广泛关注。拟采用计算机模拟和自洽场理论结合密度泛函理论研究嵌段聚合物/纳米棒嵌段体的自组装行为，分析嵌段聚合物对纳米棒取向和空间排列的影响，讨论纳米棒嵌段体的定向与协同自组装。采用模拟方法研究高分子刷诱导纳米棒/纳米颗粒共混合体系的相分离与准晶体结构，理解熵在共混体系发生相分离时起的决定性作用。研究受限条件下聚合物/纳米颗粒嵌段体的集聚与准晶体结构,讨论颗粒嵌段体大小形状等因素对准晶体结构影响。采用模拟方法研究聚合物/纳米颗粒嵌段体复合体系在剪切场时的结构和动力学过程，讨论在剪切场和纳米棒嵌段体共同影响下形成有序相结构。通过对这些问题研究，能够对复杂聚合物/纳米颗粒共混体系的自组装行为及其有序结构形成动力学过程有较深入了解。

聚合物具有丰富微观结构，纳米颗粒则具有独特的光、电、磁性质以及催化作用，因此通过在高分子基质中加入有机或无机纳米颗粒得到的高分子材料能展现其优越的电学、光学或力学性质因而在日常生活中具有非常广泛用途，备受人们关注。我们采用模拟方法研究了聚合物/二嵌段纳米棒的自组装行为，分析嵌段纳米棒的定向与协同自组装过程，讨论聚合物对纳米棒的取向与空间排列的影响以及纳米棒诱导嵌段聚合物柱状相向层状相的转变，发现这是一种特殊的层状相。采用模拟方法研究了高分子刷诱导纳米棒/纳米颗粒共混体系的相分离与纳米颗粒的准晶体结构，理解了熵在共混体系发生相分离时起的决定性作用，分析了影响这种共混体系相分离的各种因素。研究了受限于平行板中高分子刷诱导纳米颗粒相分离，实现了如何通过宏观操作对纳米颗粒微观相分离进行控制。研究了如何利用半刚性高分子链对少量数目纳米棒自组装结构进行调控，其本质是通过半刚性高分子链的螺旋结构对纳米棒结构的控制。研究了高分子链链刚性及链拓扑结构对纳米颗粒集聚行为的影响，讨论在纳米颗粒/高分子链复合物熔体中粒子间熵相互作用对链刚性以及链拓扑结构的依赖关系，发现随着高分子链刚性增加，纳米颗粒间熵相互作用随之增加并呈现各向异性。研究了纳米颗粒在半刚性环型高分子链熔体中的动力学过程与玻璃态，揭示纳米颗粒的玻璃态与环型高分子链的链刚性和浓度以及纳米颗粒大小的关系，发现随着环型高分子链刚性增加，存在着液态-玻璃态转变。通过这些纳米颗粒在聚合物基质中各种构象、集聚态以及动力学行为的研究，能够帮助我们对影响聚合物/纳米颗粒共混体系微观结构及其形成动力学过程有较深入了解。