Hierarchical Nacre Mimetics with Synergistic Mechanical Properties by Control of Molecular Interactions in Self-Healing Polymers.

Designing the reversible interactions of biopolymers remains a grand challenge for an integral mimicry of mechanically superior biological composites. Yet, they are the key to synergistic combinations of stiffness and toughness by providing sacrificial bonds with hidden length scales. To address this challenge, dynamic polymers were designed with low glass-transition temperature T(g) and bonded by quadruple hydrogen-bonding motifs, and subsequently assembled with high-aspect-ratio synthetic nanoclays to generate nacre-mimetic films. The high dynamics and self-healing of the polymers render transparent films with a near-perfectly aligned structure. Varying the polymer composition allows molecular control over the mechanical properties up to very stiff and very strong films (E≈45 GPa, σ(UTS)≈270 MPa). Stable crack propagation and multiple toughening mechanisms occur in situations of balanced dynamics, enabling synergistic combinations of stiffness and toughness. Excellent gas barrier properties complement the multifunctional property profile.

Room-Temperature Phosphorescence Enabled through Nacre-Mimetic Nanocomposite Design.

A generic, facile, and waterborne strategy is introduced to fabricate flexible, low-cost nanocomposite films with room-temperature phosphorescence (RTP) by incorporating waterborne RTP polymers into self-assembled bioinspired polymer/nanoclay nanocomposites. The excellent oxygen barrier of the lamellar nanoclay structure suppresses the quenching effect from ambient oxygen (kq ) and broadens the choice of polymer matrices towards lower glass transition temperature (Tg ), while providing better mechanical properties and processability. Moreover, the oxygen permeation and diffusion inside the films can be fine-tuned by varying the polymer/nanoclay ratio, enabling programmable retention times of the RTP signals, which is exploited for transient information storage and anti-counterfeiting materials. Additionally, anti-interception materials are showcased by tracing the interception-induced oxygen history that interferes with the preset self-erasing time. Merging bioinspired nanocomposite design with RTP materials contributes to overcoming the inherent limitations of molecular design of organic RTP compounds, and allows programmable temporal features to be added into RTP materials by controlled mesostructures. This will assist in paving the way for practical applications of RTP materials as novel anti-counterfeiting materials.

Recyclable and Light-Adaptive Vitrimer-Based Nacre-Mimetic Nanocomposites.

Nacre's natural design consists of a perfect hierarchical assembly that resembles a brick-and-mortar structure with synergistic stiffness and toughness. The field of bioinspired materials often provides attractive architecture and engineering pathways which allow to explore outstanding property areas. However, the study of nacre-mimetic materials should not be limited to the design of its architecture but ought to include the understanding, operation, and improvement of internal interactions between their components. Here, we introduce a vitrimer prepolymer system that, once integrated into the nacre-mimetic nanocomposites, cures and cross-links with the presence of Lewis acid catalyst and further manifests associative dynamic exchange reactions. Bond exchanges are controllable by molecular composition and catalyst content and characterized by creep, shear-lag, and shape-locking tests. We exploit the vitrimer properties by laminating ca. 70 films into thick bulk materials, and characterize the flexural resistance and crack propagation. More importantly, we introduce recycling by grinding and hot-pressing. The recycling for highly reinforced nacre-mimetic nanocomposites is critically enabled by the vitrimer chemistry and improves the sustainability of bioinspired nanocomposites in cyclic economy. Finally, we integrate photothermal converters into the structures and use laser irradiation as external trigger to activate the vitrimer exchange reactions.

Exceptionally Ductile and Tough Biomimetic Artificial Nacre with Gas Barrier Function.

Synthetic mimics of natural high-performance structural materials have shown great and partly unforeseen opportunities for the design of multifunctional materials. For nacre-mimetic nanocomposites, it has remained extraordinarily challenging to make ductile materials with high stretchability at high fractions of reinforcements, which is however of crucial importance for flexible barrier materials. Here, highly ductile and tough nacre-mimetic nanocomposites are presented, by implementing weak, but many hydrogen bonds in a ternary nacre-mimetic system consisting of two polymers (poly(vinyl amine) and poly(vinyl alcohol)) and natural nanoclay (montmorillonite) to provide efficient energy dissipation and slippage at high nanoclay content (50 wt%). Tailored interactions enable exceptional combinations of ductility (close to 50% strain) and toughness (up to 27.5 MJ m-3 ). Extensive stress whitening, a clear sign of high internal dynamics at high internal cohesion, can be observed during mechanical deformation, and the materials can be folded like paper into origami planes without fracture. Overall, the new levels of ductility and toughness are unprecedented in highly reinforced bioinspired nanocomposites and are of critical importance to future applications, e.g., as barrier materials needed for encapsulation and as a printing substrate for flexible organic electronics.

Facile and On-Demand Cross-Linking of Nacre-Mimetic Nanocomposites Using Tailor-Made Polymers with Latent Reactivity.

The development of on-demand cross-linking strategies is a key aspect in promoting mechanical properties of high-performance bioinspired nanocomposites. Here, we embed styrene sulfonyl azide groups with latent chemical reactivity into water-soluble copolymers and assemble those with high-aspect-ratio synthetic nanoclays to generate well-defined layered polymer/nanoclay nacre-mimetics. A considerable stiffening and strengthening occurs upon activation of the covalent cross-linking using simple heating. Varying the amount of cross-linkable units allows molecular control of mechanical properties from ductile to stiff and strong. Moreover, the covalent cross-linking enhances the moisture stability of water-borne nacre-mimetics. The strategy is facile and versatile allowing for a transfer into applications.

Cloning Nacre's 3D Interlocking Skeleton in Engineering Composites to Achieve Exceptional Mechanical Properties.

Ceramic/polymer composite equipped with 3D interlocking skeleton (3D IL) is developed through a simple freeze-casting method, exhibiting exceptionally light weight, high strength, toughness, and shock resistance. Long-range crack energy dissipation enabled by 3D interlocking structure is considered as the primary reinforcing mechanism for such superior properties. The smart composite design strategy should hold a place in developing future structural engineering materials.