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嵌段共聚物的设计、它们在纳米级结构中的集成、它们在溶液中的动力学和固-流界面自组装动力学之间的相互联系。这样，这项研究将推动自组装加工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运行的热力学控制和质量输运控制的松弛过程的相对重要性。实验研究将集中在组成和结构变化的影响上，这将通过系统地混合基于聚苯乙烯/聚异戊二烯和聚苯乙烯/聚（2-乙烯基吡啶）嵌段共聚物的各种定义良好的共聚物来介绍，这些共聚物在选择性溶剂中表现出表面活性剂样行为和自组织。形状，大小和动力学组装的混合共聚物聚集体将被充分表征。了解组成构件的组成和结构的变化将为使用简单构件的混合物来创建复杂的高阶结构铺平道路，也有助于确定通过自组装定制薄膜形成的新的有用途径。从更简单的聚合物构建块自发产生纳米结构是广泛应用于社会的各种技术的基础，包括药物封装和输送，通过溶解和动员污染物进行环境修复，以及微电子和位图形介质的图案表面的形成。这项研究有望为如何设计和加工共聚物基材料提供新的见解，以获得不同形状、尺寸和性能的组件，从而刺激额外的技术进步。此外，对溶液和界面组装动力学的了解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，该研究计划将通过在全国会议上举行的研讨会，促进青年科学家、工程师和教师的发展，并促进更大的科学界的参与。

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.