Nanograded artificial nacre with efficient energy dissipation.

The renowned mechanical performance of biological ceramics can be attributed to their hierarchical structures, wherein structural features at the nanoscale play a crucial role. However, nanoscale features, such as nanogradients, have rarely been incorporated in biomimetic ceramics because of the challenges in simultaneously controlling the material structure at multiple length scales. Here, we report the fabrication of artificial nacre with graphene oxide nanogradients in its aragonite platelets through a matrix-directed mineralization method. The gradients are formed via the spontaneous accumulation of graphene oxide nanosheets on the surface of the platelets during the mineralization process, which then induces a lateral residual stress field in the platelets. Nanoindentation tests and mercury intrusion porosimetry demonstrate that the material's energy dissipation is enhanced both intrinsically and extrinsically through the compressive stress near the platelet surface. The energy dissipation density reaches 0.159 ± 0.007 nJ/µm3, and the toughness amplification is superior to that of the most advanced ceramics. Numerical simulations also agree with the finding that the stress field notably contributes to the overall energy dissipation. This work demonstrates that the energy dissipation of biomimetic ceramics can be further increased by integrating design principles spanning multiple scales. This strategy can be readily extended to the combinations of other structural models for the design and fabrication of structural ceramics with customized and optimized performance.

Deformable hard tissue with high fatigue resistance in the hinge of bivalve Cristaria plicata.

The hinge of bivalve shells can sustain hundreds of thousands of repeating opening-and-closing valve motions throughout their lifetime. We studied the hierarchical design of the mineralized tissue in the hinge of the bivalve Cristaria plicata, which endows the tissue with deformability and fatigue resistance and consequently underlies the repeating motion capability. This folding fan-shaped tissue consists of radially aligned, brittle aragonite nanowires embedded in a resilient matrix and can translate external radial loads to circumferential deformation. The hard-soft complex microstructure can suppress stress concentration within the tissue. Coherent nanotwin boundaries along the longitudinal direction of the nanowires increase their resistance to bending fracture. The unusual biomineral, which exploits the inherent properties of each component through multiscale structural design, provides insights into the evolution of antifatigue structural materials.

Artificial Nacre with High Toughness Amplification Factor: Residual Stress-Engineering Sparks Enhanced Extrinsic Toughening Mechanisms.

The high fracture toughness of mollusk nacre is predominantly attributed to the structure-associated extrinsic mechanisms such as platelet sliding and crack deflection. While the nacre-mimetic structures are widely adopted in artificial ceramics, the extrinsic mechanisms are often weakened by the relatively low tensile strength of the platelets with a large aspect ratio, which makes the fracture toughness of these materials much lower than expected. Here, it is demonstrated that the fracture toughness of artificial nacre materials with high inorganic contents can be improved by residual stress-induced platelet strengthening, which can catalyze more effective extrinsic toughening mechanisms that are specific to the nacre-mimetic structures. Thereby, while the absolute fracture toughness of the materials is not comparable with advanced ceramic-based composites, the toughness amplification factor of the material reaches 16.1 ± 1.1, outperforming the state-of-the-art biomimetic ceramics. The results reveal that, with the merit of nacre-mimetic structural designs, the overall fracture toughness of the artificial nacre can be improved by the platelet strengthening through extrinsic toughening mechanisms, although the intrinsic fracture toughness may decrease at platelet level due to the strengthening. It is anticipated that advanced structural ceramics with exceeding performance can be fabricated through these unconventional strategies.

Lightweight, tough, and sustainable cellulose nanofiber-derived bulk structural materials with low thermal expansion coefficient.

Sustainable structural materials with light weight, great thermal dimensional stability, and superb mechanical properties are vitally important for engineering application, but the intrinsic conflict among some material properties (e.g., strength and toughness) makes it challenging to realize these performance indexes at the same time under wide service conditions. Here, we report a robust and feasible strategy to process cellulose nanofiber (CNF) into a high-performance sustainable bulk structural material with low density, excellent strength and toughness, and great thermal dimensional stability. The obtained cellulose nanofiber plate (CNFP) has high specific strength [~198 MPa/(Mg m-3)], high specific impact toughness [~67 kJ m-2/(Mg m-3)], and low thermal expansion coefficient (<5 × 10-6 K-1), which shows distinct and superior properties to typical polymers, metals, and ceramics, making it a low-cost, high-performance, and environmental-friendly alternative for engineering requirement, especially for aerospace applications.

Bioinspired polymeric woods.

Woods provide bioinspiration for engineering materials due to their superior mechanical performance. We demonstrate a novel strategy for large-scale fabrication of a family of bioinspired polymeric woods with similar polyphenol matrix materials, wood-like cellular microstructures, and outstanding comprehensive performance by a self-assembly and thermocuring process of traditional resins. In contrast to natural woods, polymeric woods demonstrate comparable mechanical properties (a compressive yield strength of up to 45 MPa), preferable corrosion resistance to acid with no decrease in mechanical properties, and much better thermal insulation (as low as ~21 mW m-1 K-1) and fire retardancy. These bioinspired polymeric woods even stand out from other engineering materials such as cellular ceramic materials and aerogel-like materials in terms of specific strength and thermal insulation properties. The present strategy provides a new possibility for mass production of a series of high-performance biomimetic engineering materials with hierarchical cellular microstructures and remarkable multifunctionality.

[Study on the stability variation mechanism of humic acid water solution after radiated by the UV light].

Humic acid widely presents in various surface waters. Molecular structure has significant impacts on its physical and chemical properties. To explore the stability variation of humic acid before and after the UV light radiation, spectroscopic and electrochemical analysis were applied in this paper. Structural parameters selected in the experiments include reactive sites, such as phenolic hydroxyl and carboxyl contents, Zeta potential, and colloidal size. It was found that there was little humic acid being removed in the solution without UV radiation pretreatment; while its remove ratio increased notably with radiation time. After 3 h pretreatment, humic acid removal ratio was above 80% in coagulation. Spectroscopy analysis results showed that partial of the groups with fluorescent effects might be shed or rearranged after the radiation; while its aromatic structure was not destroyed. Both the Zeta potential and average colloidal size decreased with the radiation time, which was not conducive to the aggregation of humic acid. However, -OH content decreased slightly after the UV radiation, and new carboxyl and carbonyl groups formed simultaneously. The increasing of the reactive sites and the improvement of the reaction effectiveness were the major reasons leading to humic acid stability decrease in PAC! coagulation.

Site-selective photoinduced electron transfer from alcoholic solvents to the chromophore facilitated by hydrogen bonding: a new fluorescence quenching mechanism.

Solute-solvent intermolecular photoinduced electron transfer (ET) reaction was proposed to account for the drastic fluorescence quenching behaviors of oxazine 750 (OX750) chromophore in protic alcoholic solvents. According to our theoretical calculations for the hydrogen-bonded OX750-(alcohol)(n) complexes using the time-dependent density functional theory (TDDFT) method, we demonstrated that the ET reaction takes place from the alcoholic solvents to the chromophore and the intermolecular ET passing through the site-specific intermolecular hydrogen bonds exhibits an unambiguous site selectivity. In our motivated experiments of femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD), it could be noted that the ultrafast ET reaction takes place as fast as 200 fs. This ultrafast intermolecular photoinduced ET is much faster than the diffusive solvation process, and even significantly faster than the intramolecular vibrational redistribution (IVR) process of the OX750 chromophore. Therefore, the ultrafast intermolecular ET should be coupled with the hydrogen-bonding dynamics occurring in the sub-picosecond time domain. We theoretically demonstrated for the first time that the selected hydrogen bonds are transiently strengthened in the excited states for facilitating the ultrafast solute-solvent intermolecular ET reaction.

Starlike nanostructures of polyoxometalates K3[PMo12O40].nH2O synthesized and assembled by an inverse microemulsion method.

In a nonionic inverse microemulsion system, surfactant (C12-18EO9)/cyclohexane/water, heteropolyanions [PMo12O40]3- react with K+ to form K3[PMo12O40].nH2O nanorods and assemble as three-dimensional starlike nanostructures.