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Due to their low damage tolerance, engineering ceramic foams are often limited to non-structural usages. In this work, we report that stereom, a bioceramic cellular solid (relative density, 0.2–0.4) commonly found in the mineralized skeletal elements of echinoderms (e.g., sea urchin spines), achieves simultaneous high relative strength which approaches the Suquet bound and remarkable energy absorption capability (ca. 17.7 kJ kg⁻¹) through its unique bicontinuous open-cell foam-like microstructure. The high strength is due to the ultra-low stress concentrations within the stereom during loading, resulted from their defect-free cellular morphologies with near-constant surface mean curvatures and negative Gaussian curvatures. Furthermore, the combination of bending-induced microfracture of branches and subsequent local jamming of fractured fragments facilitated by small throat openings in stereom leads to the progressive formation and growth of damage bands with significant microscopic densification of fragments, and consequently, contributes to stereom’s exceptionally high damage tolerance.

Biomineralized composites, which are usually composed of microscopic mineral building blocks organized in 3D intercrystalline organic matrices, have evolved unique structural designs to fulfill mechanical and other biological functionalities. While it has been well recognized that the intricate architectural designs of biomineralized composites contribute to their remarkable mechanical performance, the structural features within and corresponding mechanical properties of individual mineral building blocks are often less appreciated in the context of bio‐inspired structural composites. The mineral building blocks in biomineralized composites exhibit a variety of salient intracrystalline structural features, such as, organic inclusions, inorganic impurities (or trace elements), crystalline features (e.g., amorphous phases, single crystals, splitting crystals, polycrystals, and nanograins), residual stress/strain, and twinning, which significantly modify the mechanical properties of biogenic minerals. In this review, recent progress in elucidating the intracrystalline structural features of three most common biomineral systems (calcite, aragonite, and hydroxyapatite) and their corresponding mechanical significance are discussed. Future research directions and corresponding challenges are proposed and discussed, such as the advanced structural characterizations and formation mechanisms of intracrystalline structures in biominerals, amorphous biominerals, and bio‐inspired synthesis.

Biomineralized materials are sophisticated material systems with hierarchical 3D material architectures, which are broadly used as model systems for fundamental mechanical, materials science, and biomimetic studies. The current knowledge of the structure of biological materials is mainly based on 2D imaging, which often impedes comprehensive and accurate understanding of the materials’ intricate 3D microstructure and consequently their mechanics, functions, and bioinspired designs. The development of 3D techniques such as tomography, additive manufacturing, and 4D testing has opened pathways to study biological materials fully in 3D. This review discusses how applying 3D techniques can provide new insights into biomineralized materials that are either well known or possess complex microstructures that are challenging to understand in the 2D framework. The diverse structures of biomineralized materials are characterized based on four universal structural motifs. Nacre is selected as an example to demonstrate how the progression of knowledge from 2D to 3D can bring substantial improvements to understanding the growth mechanism, biomechanics, and bioinspired designs. State‐of‐the‐art multiscale 3D tomographic techniques are discussed with a focus on their integration with 3D geometric quantification, 4D in situ experiments, and multiscale modeling. Outlook is given on the emerging approaches to investigate the synthesis–structure–function–biomimetics relationship.