High Performance Nacre Fibers by Engineering Interfacial Entanglement.

Biological materials exhibit fascinating mechanical properties for intricate interactions at multiple interfaces to combine superb toughness with wondrous strength and stiffness. Recently, strong interlayer entanglement has emerged to replicate the powerful dissipation of natural proteins and alleviate the conflict between strength and toughness. However, designing intricate interactions in a strong entanglement network needs to be further explored. Here, we modulate interlayer entanglement by introducing multiple interactions, including hydrogen and ionic bonding, and achieve ultrahigh mechanical performance of graphene-based nacre fibers. Two essential modulating trends are directed. One is modulating dynamic hydrogen bonding to improve the strength and toughness up to 1.58 GPa and 52 MJ/m3, simultaneously. The other is tailoring ionic coordinating bonding to raise the strength and stiffness, reaching 2.3 and 253 GPa. Modulating various interactions within robust entanglement provides an effective approach to extend performance limits of bioinspired nacre and optimize multiscale interfaces in diverse composites.

Hydrogen bonding-regulated miscibility of graphene oxide and nonionic water-soluble polymers.

The integration of graphene and nonionic water-soluble polymers has generated useful composites with high performances and rich functionalities. These attractive graphene composites are usually synthesized from the aqueous mixture of graphene oxide (GO) precursor and polymers such as synthetic polyvinyl alcohol and natural cellulose. In this widely known preparation method, the miscibility of GO and nonionic water-soluble polymers seems to be intuitive but has been disputed by some observations of gelation and aggregation. Herein, we have re-examined the miscibility of GO and nonionic water-soluble polymers and confirm their general coaggregation caused by hydrogen bonding interaction. Due to the increasing GO concentration, the property of stable miscibility is converted to aggregation by surface adsorption with transient hydrogen bond crosslinking. We have proposed a preheat mixing strategy to prepare a homogenous solution of GO and nonionic water-soluble polymers in any arbitrary ratio. The re-exploited miscibility allows the fabrication of homogeneous composite papers with renewed high performance trend. The hydrogen bonding-regulated miscibility refreshes the understanding on graphene/water-soluble polymeric composites and provides an ecofriendly interaction control method to modulate the assembly of structures and materials.

Vertical Array of Graphite Oxide Liquid Crystal by Microwire Shearing for Highly Thermally Conductive Composites.

Excellent through-plane thermally conductive composites are highly demanded for efficient heat dissipation. Giant sheets have large crystalline domain and significantly reduce interface phonon scattering, making them promising to build highly thermally conductive composites. However, realizing vertical orientation of giant sheets remains challenging due to their enormous mass and huge hydrodynamic drag force. Here, we achieve highly vertically ordered liquid crystals of giant graphite oxide (more than 100 µm in lateral dimension) by microwire shearing, which endows the composite with a recorded through-plane thermal conductivity of 94 W m-1 K-1 . Microscale shearing fields induced by vertical motion of microwires conquer huge hydrodynamic energy barrier and vertically reorient giant sheets. The resulting liquid crystals exhibit extremely retarded relaxation and impart large-scale vertical array with bidirectional ordering degree as high as 0.82. The graphite array-based composites demonstrate an ultrahigh thermal enhancement efficiency of over 35 times per unit volume. Furthermore, the composites improve cooling efficiency by 93% for thermal management tests compared to commercial thermal interface materials. This work offers a novel methodology to precisely manipulate the orientation of giant particles and promote large-scale fabrication of vertical array with advanced functionalities.

Monodomain Liquid Crystals of Two-Dimensional Sheets by Boundary-Free Sheargraphy.

Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials. However, liquid crystals are metastable and sensitive to external stimuli, such as flow, confinement, and electromagnetic fields, which cause their intrinsic polycrystallinity and topological defects. Here, we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy. The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets, which has the same optical polarized angle and intensity. The monodomain liquid crystals provide bidirectionally ordered skeletons, which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity. Furthermore, we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals. Topological structures with defect strength from - 2 to + 2 were realized. This work provides a facile methodology to study the structural order of soft matter at a macroscopic level, facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.

Hydroplastic Micromolding of 2D Sheets.

Processing 2D sheets into desired structures with high precision is of great importance for fabrication and application of their assemblies. Solution processing of 2D sheets from dilute dispersions is a commonly used method but offers limited control over feature size precision owing to the extreme volume shrinkage. Plastic processing from the solid state is therefore a preferable approach to achieve high precision. However, plastic processing is intrinsically hampered by strong interlayer interactions of the 2D sheet solids. Here, a hydroplastic molding method to shape layered solids of 2D sheets with micrometer-scale precision under ambient conditions is reported. The dried 2D layered solids are plasticized by intercalated solvents, affording plastic near-solid compounds that enable local plastic deformation. Such an intercalated solvent-induced hydroplasticity is found in a broad family of 2D materials, for example graphene, MoS2 , and MXene. The hydroplastic molding enables fabrication of complex spatial structures (knurling, origami) and microimprinted tubular structures down to diameters of 390 nm with good fidelity. The method enhances the structural accuracy and enriches the structural diversity of 2D macroassemblies, thus providing a feasible strategy to tune their electrical, optical, and other functional properties.

Precise Thermoplastic Processing of Graphene Oxide Layered Solid by Polymer Intercalation.

The processing capability is vital for the wide applications of materials to forge structures as-demand. Graphene-based macroscopic materials have shown excellent mechanical and functional properties. However, different from usual polymers and metals, graphene solids exhibit limited deformability and processibility for precise forming. Here, we present a precise thermoplastic forming of graphene materials by polymer intercalation from graphene oxide (GO) precursor. The intercalated polymer enables the thermoplasticity of GO solids by thermally activated motion of polymer chains. We detect a critical minimum containing of intercalated polymer that can expand the interlayer spacing exceeding 1.4 nm to activate thermoplasticity, which becomes the criteria for thermal plastic forming of GO solids. By thermoplastic forming, the flat GO-composite films are forged to Gaussian curved shapes and imprinted to have surface relief patterns with size precision down to 360 nm. The plastic-formed structures maintain the structural integration with outstanding electrical (3.07 × 105 S m-1) and thermal conductivity (745.65 W m-1 K-1) after removal of polymers. The thermoplastic strategy greatly extends the forming capability of GO materials and other layered materials and promises versatile structural designs for more broad applications.