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

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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.