Advancing Self-Assembly Processing through Architecturally- and Compositionally-Complex Block Copolymer Surfactant Mixtures

本研究的目的是阐明结构复杂的嵌段共聚物的设计，它们的集成到纳米级结构，它们在溶液中的动力学和固-液界面自组装动力学之间的相互联系。 通过这样做，这项研究将推进自组装工艺作为纳米制造的一种手段。 这项工作的一个独特和新颖的方面涉及使用动力学建模来量化在固-液界面自组装过程中操作的物质控制和质量输运管理的松弛过程的相对重要性。 实验研究将集中在组合物和结构的变化，这将是通过系统地混合不同的集合的定义明确的共聚物的基础上，聚苯乙烯/聚异戊二烯和聚苯乙烯/聚（2-乙烯基吡啶）嵌段共聚物，显示表面活性剂样的行为和自组织的选择性溶剂的影响。 将充分表征混合共聚物聚集体的形状、尺寸和组装动力学。 了解组成构件的组成和结构的变化将如何为使用较简单构件的混合物来创建复杂的高阶结构铺平道路，并且还有助于识别新的和有用的途径，用于通过自-从较简单的聚合物结构单元自发产生纳米结构是在社会中应用的各种技术的基础，包括药物封装和递送、通过污染物的溶解和移动的环境修复、以及用于微电子和位图案化介质的图案化表面的形成。 这项研究有望为如何设计和加工基于共聚物的材料提供新的见解，以获得不同形状，尺寸和性能的组件，从而促进更多的技术进步。 此外，在溶液中和界面处组装的动力学知识将促进自组装作为纳米制造形式的发展，这为通过有效和可扩展的方法创造新产品，结构和设备提供了有趣的可能性。 最后，该研究方案将促进青年科学家、工程师和教师的发展，并将通过在一次全国会议上举行的专题讨论会，使更广大的科学界参与进来。

The objective of this research is to elucidate the interconnected links between the design of architecturally-complex block copolymers, their integration into nanoscale structures, their dynamics in solution and kinetics of self-assembly at solid-fluid interfaces. In so doing, this research will advance self-assembly processing as a means of nano-manufacturing. A distinctive and novel aspect of the work involves the use of kinetic modeling to quantify the relative importance of thermodynamically-controlled and mass transport-governed relaxation processes that operate during self-assembly at solid-fluid interfaces. Experimental studies will focus on the effect of variations in composition and architecture, which will be introduced by systematically mixing diverse sets of well-defined copolymers based on polystyrene/polyisoprene and polystyrene/poly(2-vinylpyridine) block copolymers, which display surfactant-like behaviors and self-organize in selective solvents. The shape, size, and kinetics of assembly of the mixed copolymer aggregates will be fully characterized. Understanding how variations in the composition and architecture of the constituent building blocks will pave the way for using mixtures of simpler building blocks to create complex, higher-order structures, and also help to identify new and useful pathways for tailoring thin film formation by self-assembly.The spontaneous generation of nanostructures from simpler polymeric building blocks is fundamental to a wide variety of technologies finding application in society, including drug encapsulation and delivery, environmental remediation by solubilization and mobilization of contaminants, and formation of patterned surfaces for microelectronics and bit-patterned media. This research promises to provide new insights into how to design and process copolymer-based materials to attain assemblies of different shape, size, and properties, thereby spurring additional technological advances. In addition, knowledge of the kinetics of assembly in solution and at interfaces will enhance the development of self-assembly as form of nano-manufacturing, which offers intriguing possibilities for creating new products, structures and devices via an efficient and scalable method. Finally, this research program will foster the development of young scientists, engineers and teachers, and the greater scientific community will be engaged through a symposium conducted at a national meeting.