Self-Assembled Bioinspired Nanocomposites.

Bioinspired materials engineering impacts the design of advanced functional materials across many domains of sciences from wetting behavior to optical and mechanical materials. In all cases, the advances in understanding how biology uses hierarchical design to create failure and defect-tolerant materials with emergent properties lays the groundwork for engaging into these topics. Biological mechanical materials are particularly inspiring for their unique combinations of stiffness, strength, and toughness together with lightweightness, as assembled and grown in water from a limited set of building blocks at room temperature. Wood, nacre, crustacean cuticles, and spider silk serve as some examples, where the correct arrangement of constituents and balanced molecular energy dissipation mechanisms allows overcoming the shortcomings of the individual components and leads to synergistic materials performance beyond additive behavior. They constitute a paradigm for future structural materials engineering-in the formation process, the use of sustainable building blocks and energy-efficient pathways, as well as in the property profiles-that will in the long term allow for new classes of high-performance and lightweight structural materials needed to promote energy efficiency in mobile technologies.This Account summarizes our efforts of the past decade with respect to designing self-assembling bioinspired materials aiming for both mechanical high-performance structures and new types of multifunctional property profiles. The Account is set out to first give a definition of bioinspired nanocomposite materials and self-assembly therein, followed by an in-depth discussion on the understanding of mechanical performance and rational design to increase the mechanical performance. We place a particular emphasis on materials formed at high fractions of reinforcements and with tailor-made functional polymers using self-assembly to create highly ordered structures and elucidate in detail how the soft polymer phase needs to be designed in terms of thermomechanical properties and sacrificial supramolecular bonds. We focus on nanoscale reinforcements such as nanoclay and nanocellulose that lead to high contents of internal interfaces and intercalated polymer layers that experience nanoconfinement. Both aspects add fundamental challenges for macromolecular design of soft phases using precision polymer synthesis. We build upon those design criteria and further develop the concepts of adaptive bioinspired nanocomposites, whose properties are switchable from the outside using molecularly defined triggers with light. In a last section, we discuss how new types of functional properties, in particular flexible and transparent gas barrier materials or fire barrier materials, can be reached on the basis of the bioinspired nanocomposite design strategies. Additionally, we show new types of self-assembled photonic materials that can even be evolved into self-assembling lasers, hence moving the concept of mechanical nanocomposite design to other functionalities.The comparative discussion of different bioinspired nanocomposite architectures with nematic, fibrillar, and cholesteric structures, as based on different reinforcing nanoparticles, aims for a unified understanding of the design principles and shall aid researchers in the field in the more elaborate design of future bioinspired nanocomposite materials based on molecular control principles. We conclude by addressing challenges, in particular also the need for a transfer from fundamental molecular materials science into scalable engineering materials of technological and societal relevance.