Crystal orientation mapping and microindentation reveal anisotropy in Porites skeletons.

Structures made by scleractinian corals support diverse ocean ecosystems. Despite the importance of coral skeletons and their predicted vulnerability to climate change, few studies have examined the mechanical and crystallographic properties of coral skeletons at the micro- and nano-scales. Here, we investigated the interplay of crystallographic and microarchitectural organization with mechanical anisotropy within Porites skeletons by measuring Young's modulus and hardness along surfaces transverse and longitudinal to the primary coral growth direction. We observed micro-scale anisotropy, where the transverse surface had greater Young's modulus and hardness by ∼ 6 GPa and 0.2 GPa, respectively. Electron backscatter diffraction (EBSD) revealed that this surface also had a higher percentage of crystals oriented with the a-axis between ± 30-60∘, relative to the longitudinal surface, and a broader grain size distribution. Within a region containing a sharp microscale gradient in Young's modulus, nanoscale indentation mapping, energy dispersive spectroscopy (EDS), EBSD, and Raman crystallography were performed. A correlative trend showed higher Young's modulus and hardness in regions with individual crystal bases (c-axis) facing upward, and in crystal fibers relative to centers of calcification. These relationships highlight the difference in mechanical properties between scales (i.e. crystals, crystal bundles, grains). Observations of crystal orientation and mechanical properties suggest that anisotropy is driven by microscale organization and crystal packing rather than intrinsic crystal anisotropy. In comparison with previous observations of nanoscale isotropy in corals, our results illustrate the role of hierarchical architecture in coral skeletons and the influence of biotic and abiotic factors on mechanical properties at different scales. STATEMENT OF SIGNIFICANCE: Coral biomineralization and the ability of corals' skeletal structure to withstand biotic and abiotic forces underpins the success of reef ecosystems. At the microscale, we show increased skeletal stiffness and hardness perpendicular to the coral growth direction. By comparing nano- and micro-scale indentation results, we also reveal an effect of hierarchical architecture on the mechanical properties of coral skeletons and hypothesize that crystal packing and orientation result in microscale anisotropy. In contrast to previous findings, we demonstrate that mechanical and crystallographic properties of coral skeletons can vary between surface planes, within surface planes, and at different analytical scales. These results improve our understanding of biomineralization and the effects of scale and direction on how biomineral structures respond to environmental stimuli.

Multi-scale structural design and biomechanics of the pistol shrimp snapper claw.

The Arthropoda, the largest phylum of the Animal Kingdom, have successfully evolved to survive various ecological constraints under a wide range of environmental conditions. Central to this survival are the structural designs developed in their exoskeletons and their raptorial appendages for protection and hunting. One such example, the pistol shrimp, is a shallow-water crustacean that is well-known for its aggressive hunting behavior, using its snapper claw to trigger the nucleation of cavitation bubbles that strike targets. In this study, we conducted a multi-scale structural/nanomechanics relationship study of this biotool to analyze its mechanical response to contact stresses. We found that the pistol shrimp snapper claw, which exhibits the capacity to emit a high-velocity water jet during rapid closure actions, is more brittle than other mineralized biotools, exhibiting accelerated wear damage under contact stresses. However, due to an angular offset between the dactylus and pollex of the snapper claw, the appendage never engages in any mechanical contact during the snapping action. This feature is in stark contrast to that reported in other fast raptorial appendages of crustaceans, notably the mantis shrimp dactyl club, which is designed to shatter close range targets in contact mode and exhibits a superior resistance to contact damage and wear. These findings suggest that adaptation of hunting appendages goes beyond their macroscopic morphology, and that multi-scale structural design concomitantly adapted to function, with enhanced structural complexification for tools that are subjected to more intense contact stresses. STATEMENT OF SIGNIFICANCE: The evolution success of crustaceans is largely due to the diversification of their mineralized exoskeletons and hunting appendages, which exhibit a large palette of morphometric characteristics that have adapted to meet particular functions. We explored the "snapper claw" of the pistol shrimp, which is used to generate cavitation bubbles and strike prey. Our multi-scale structure-property relationship study reveals that the snapper claw is more brittle than other fast raptorial appendages - such as the stomatopod dactyl club - because it is not directly subjected to direct contact forces during action. This study implies that when higher mechanical stresses are needed to meet the function, the internal structure is built of a more complex architecture that allows to mitigate internal structural damage.

Parrotfish Teeth: Stiff Biominerals Whose Microstructure Makes Them Tough and Abrasion-Resistant To Bite Stony Corals.

Parrotfish (Scaridae) feed by biting stony corals. To investigate how their teeth endure the associated contact stresses, we examine the chemical composition, nano- and microscale structure, and the mechanical properties of the steephead parrotfish Chlorurus microrhinos tooth. Its enameloid is a fluorapatite (Ca5(PO4)3F) biomineral with outstanding mechanical characteristics: the mean elastic modulus is 124 GPa, and the mean hardness near the biting surface is 7.3 GPa, making this one of the stiffest and hardest biominerals measured; the mean indentation yield strength is above 6 GPa, and the mean fracture toughness is ∼2.5 MPa·m1/2, relatively high for a highly mineralized material. This combination of properties results in high abrasion resistance. Fluorapatite X-ray absorption spectroscopy exhibits linear dichroism at the Ca L-edge, an effect that makes peak intensities vary with crystal orientation, under linearly polarized X-ray illumination. This observation enables polarization-dependent imaging contrast mapping of apatite, a method to quantitatively measure and display nanocrystal orientations in large, pristine arrays of nano- and microcrystalline structures. Parrotfish enameloid consists of 100 nm-wide, microns long crystals co-oriented and assembled into bundles interwoven as the warp and the weave in fabric and therefore termed fibers here. These fibers gradually decrease in average diameter from 5 µm at the back to 2 µm at the tip of the tooth. Intriguingly, this size decrease is spatially correlated with an increase in hardness.