Nature has evolved efficient strategies to synthesize complex mineralized structures that exhibit exceptional damage tolerance. One such example is found in the hypermineralized hammer-like dactyl clubs of the stomatopods, a group of highly aggressive marine crustaceans. The dactyl clubs from one species, Odontodactylus scyllarus, exhibit an impressive set of characteristics adapted for surviving high-velocity impacts on the heavily mineralized prey on which they feed. Consisting of a multiphase composite of oriented crystalline hydroxyapatite and amorphous calcium phosphate and carbonate, in conjunction with a highly expanded helicoidal organization of the fibrillar chitinous organic matrix, these structures display several effective lines of defense against catastrophic failure during repetitive high-energy loading events.
Over millions of years, the crustacean exoskeleton has evolved into a rigid, tough, and complex cuticle that is used for structural support, mobility, protection of vital organs, and defense against predation. The crustacean cuticle is characterized by a hierarchically arranged chitin fiber scaffold, mineralized predominately by calcium carbonate and/or calcium phosphate. The structural organization of the mineral and organic within the cuticle occurs over multiple length scales, resulting in a strong and tough biological composite. Here, the ultrastructural details observed in three species of crustacean are reviewed: the American lobster (Homarus americanus), the edible crab (Cancer pagurus), and the peacock mantis shrimp (Odontodactylus scyllarus). The Review concludes with a discussion of recent advances in the development of biomimetics with controlled organic scaffolding, mineralization, and the construction of nanoscale composites, inspired by the organization and formation of the crustacean cuticle.
Ecological pressures and varied feeding behaviors in a multitude of organisms have necessitated the drive for adaptation. One such change is seen in the feeding appendages of stomatopods, a group of highly predatory marine crustaceans. Stomatopods include "spearers," who ambush and snare soft bodied prey, and "smashers," who bludgeon hard-shelled prey with a heavily mineralized club. The regional substructural complexity of the stomatopod dactyl club from the smashing predator Odontodactylus scyllarus represents a model system in the study of impact tolerant biominerals. The club consists of a highly mineralized impact region, a characteristic Bouligand architecture (common to arthropods), and a unique section of the club, the striated region, composed of highly aligned sheets of mineralized fibers. Detailed ultrastructural investigations of the striated region within O. scyllarus and a related species of spearing stomatopod, Lysiosquillina maculate show consistent organization of mineral and organic, but distinct differences in macro-scale architecture. Evidence is provided for the function and substructural exaptation of the striated region, which facilitated redeployment of a raptorial feeding appendage as a biological hammer. Moreover, given the need to accelerate underwater and "grab" or "smash" their prey, the spearer and smasher appendages are specifically designed with a significantly reduced drag force.
Magnesium nanoparticles (NPs) offer the potential of high-performance reactive materials from both thermodynamic and kinetic perspectives. However, the fundamental energy release mechanisms and kinetics have not been explored due to the lack of facile synthetic routes to high-purity Mg NPs. Here, a vapor-phase route to surface-pure, core−shell nanoscale Mg particles is presented, whereby controlled evaporation and growth are utilized to tune particle sizes (40−500 nm), and their size-dependent reactivity and energetic characteristics are evaluated. Extensive in situ characterizations shed light on the fundamental reaction mechanisms governing the energy release of Mg NP-based energetic composites across particle sizes and oxidizer chemistries. Direct observations from in situ transmission electron microscopy and high-speed temperature-jump/time-of-flight mass spectrometry coupled with ignition characterization reveal that the remarkably high reactivity of Mg NPs is a direct consequence of enhanced vaporization and Mg release from their high-energy surfaces that result in the accelerated energy release kinetics from their composites. Mg NP composites also demonstrate mitigated agglomeration and sintering during reaction due to rapid gasification, enabling complete energy extraction from their oxidation. This work expands the compositional possibilities of nanoscale solid fuels by highlighting the critical relationships between metal volatilization and oxidative energy release from Mg NPs, thus opening new opportunities for strategic design of functional Mg-based nanoenergetic materials for tunable energy release.
Mantis shrimp are aggressive marine crustaceans well known for their rapid and powerful hunting strategies. Less well known, however, is the ability of some species of mantis shrimp to defend themselves from the repeated blows of conspecifics during ritualized fighting using a shield-like segment of abdominal armor called the telson. Multiscale structure-mechanical property relationships of this damage-tolerant biological composite is examined in order to reveal strategies that nature uses for resisting failure from repeated high-energy impacts. The telson structures of the smashingtype species, Odontodactylus scyllarus, and the less aggressive spearing-type species, Lysiosquillina maculata, are compared in order to better understand the ecological pressures driving the formation and use of the telson as a biological shield. A higher bulk compressive stiffness is identified within the smasher telson, which is attributed to its concave macromorphology, thicker cuticle, and higher degree of mineralization within its exocuticle. The presence of ridges at the dorsal surface suggests a role in imparting compliance for energy absorption. Fracture analysis identifies an enhanced toughening mechanism of crack twisting within the smasher telson, attributed to its well-defined pitch-graded helicoidal fibrous micro-architecture. Such findings may prove useful for the design of lightweight composite materials with potential flexibility and improved damage tolerance.
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