The combination of soft nanoscale organic components with inorganic nanograins hierarchically designed by natural organisms results in highly ductile structural materials that can withstand mechanical impact and exhibit high resilience on the macro- and nano-scale. Our investigation of nacre deformation reveals the underlying nanomechanics that govern the structural resilience and absorption of mechanical energy. Using high-resolution scanning/transmission electron microscopy (S/TEM) combined with in situ indentation, we observe nanoscale recovery of heavily deformed nacre that restores its mechanical strength on external stimuli up to 80% of its yield strength. Under compression, nacre undergoes deformation of nanograins and non-destructive locking across organic interfaces such that adjacent inorganic tablets structurally join. The locked tablets respond to strain as a continuous material, yet the organic boundaries between them still restrict crack propagation. Remarkably, the completely locked interface recovers its original morphology without any noticeable deformation after compressive contact stresses as large as 1.2 GPa.

Abstract. The intertidal bivalve Katelysia rhytiphora, endemic to south Australia and Tasmania, is used here for pulsed Sr-labelling experiments in aquaculture experiments to visualize shell growth at the micro- to nanoscale. The ventral margin area of the outer shell layer composed of (i) an outermost outer shell layer (oOSL) with compound composite prismatic architecture with three hierarchical orders of prisms and (ii) an innermost outer shell layer (iOSL) with crossed-acicular architecture consisting of intersecting lamellae bundles. All structural orders in both layers are enveloped by an organic sheath and the smallest mineralized units are nano-granules. Electron backscatter diffraction reveals a strong preferred orientation of the aragonite c axes perpendicular to the growth layers, while the a and b axes are scattered within a plane normal to the local growth direction and >46 % twin grain boundaries are detected. The Young's modulus shows a girdle-like maximum of elastically stiffer orientations for the shell following the inner shell surface. For 6 d, the bivalves were subjected twice to seawater with an increased Sr concentration of 18× mean ocean water by dissolving 144 µg g−1 Sr (159.88 Sr∕Ca mmol ∕ mol) in seawater. The pulse labelling intervals in the shell are 17× (oOSL) and 12× (iOSL) enriched in Sr relative to the Sr-spiked seawater. All architectural units in the shell are transected by the Sr label, demonstrating shell growth to progress homogeneously instead of forming one individual architectural unit after the other. Distribution coefficients, DSr ∕ Ca, for labelled and unlabelled shells are similar to shell proportions formed in the wild (0.12 to 0.15). All DSr ∕ Ca values are lower than values for equilibrium partitioning of Sr in synthetic aragonite.

Photo‐induced force microscopy (PiFM) is a new‐frontier technique that combines the advantages of atomic force microscopy with infrared spectroscopy and allows for the simultaneous acquisition of 3D topographic data with molecular chemical information at high spatial (~ 5 nm) and spectral (~ 1 cm−1) resolution at the nanoscale. This non‐destructive technique is time efficient as it requires only conventional mirror‐polishing and has fast mapping rates on the order of a few minutes that allow the study of dynamic processes via time series. Here, we review the method’s historical development, working principle, data acquisition, and evaluation, and provide a comparison with traditional geochemical methods. We review PiFM studies in the areas of materials science, chemistry and biology. In addition, we provide the first applications for geochemical samples including the visualization of faint growth zonation in zircons, the identification of fluid speciation in high‐pressure experimental samples, and of nanoscale organic phases in biominerals. We demonstrate that PiFM analysis is a time‐ and cost‐efficient technique combining high‐resolution surface imaging with molecular chemical information at the nanoscale and, thus, complements and expands traditional geochemical methods.

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