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Crustaceanderived biomimetic components and nanostructured composites
... Several reviews have summarized ongoing research and prospects on the subject. Grunenfelder et al. [148] detail three biological models, using the American lobster (Homarus americanus), the edible crab (Cancer pagurus), and the peacock mantis shrimp (Odontodactylus scyllarus). They propose different directions for the creation of nanoscale composite biomimetics, from chitin-based scaffolds to synthetic polymer templates. ...
... Biomimetic composites have potential applications in armor design, architecture, and aerospace and automotive industries, where lightweight structures with high strength and toughness are required. Crustacean cuticle ultrastructure has inspired high-performance composite components, as reviewed by Grunenfelder et al. [148]. Reinforcement with chitin whiskers to increase tensile strength and resistance to deformation under constraints (Young's modulus) has led to reinforced plastics. ...
« With its integral treatment of ecosystem and resource management, this is the only overview of the field to address current thinking and future trends. All contributions have been written with the novice in mind, explaining the basics and highlighting recent developments and achievements.
Unmatched in scope, this two-volume reference covers both traditional and well-established areas of marine biotechnology, such as biomass production, alongside such novel ones as biofuels, biological protection of structures and bioinspired materials. In so doing, it ties together information usually only found in widely dispersed sources to assemble a grand unified view of the current state of and prospects for this multi-faceted discipline.
The combination of the breadth of topics and the focus on modern ideas make this introductory book especially suitable for teaching purposes and for guiding newcomers to the many possibilities offered by this booming field”.
... Several reviews have summarized ongoing research and prospects on the subject. Grunenfelder et al. [148] detail three biological models, using the American lobster (Homarus americanus), the edible crab (Cancer pagurus), and the peacock mantis shrimp (Odontodactylus scyllarus). They propose different directions for the creation of nanoscale composite biomimetics, from chitin-based scaffolds to synthetic polymer templates. ...
... Biomimetic composites have potential applications in armor design, architecture, and aerospace and automotive industries, where lightweight structures with high strength and toughness are required. Crustacean cuticle ultrastructure has inspired high-performance composite components, as reviewed by Grunenfelder et al. [148]. Reinforcement with chitin whiskers to increase tensile strength and resistance to deformation under constraints (Young's modulus) has led to reinforced plastics. ...
Biomineralization is a biologically controlled process by which available inorganic ions are extracted from the medium toward the production of solid structures that offer an adaptive advantage to the producing organism. Fossilization is also a form of biomineralization. In the sea, these structures range from monolithic crystals produced by bacteria to architectured organomineral composites produced by a majority of protists, plants, and animals. Their production can originate internally in specialized organelles or occur externally, and they can perform mechanical/structural or functional/defensive roles. Most biominerals outlive their biological host and eventually accumulate through time, modifying the biogeochemistry of the ocean floor and of the lithosphere in general. This chapter is an overview of the three major types of marine biominerals (calcium carbonate, silica, heavy metals), the organisms that produce them (bacteria, cyanobacteria, protozoans, phytoplankton, seaweeds, protostomia invertebrates, deuterostomia invertebrates, fish), and their use in novel biotechnologies (industry, medicine, nanotechnology). Interest in biomineralization lies in the fact that organisms can produce intricate biominerals under mild, ambient conditions, in contrast to their production by conventional chemical synthesis. Observing why and how organisms invest in producing specific biominerals may be very rewarding as a source of bioinspiration. Biominerals are important for human health and welfare in a biotechnology era that has to face the multiple challenges of global warming, with its threats to species diversity and habitat loss.
... This dichotomy has been addressed in nature through the evolution of incredibly strong, fracture resistant structures by using soft-hard interfaces [33]. Examples of soft-hard interfaces include the bone density of the acorn woodpecker [34], mollusc nacre [35,36], turtle shell suture bonds [33,37] and the skeletal arrangements of lobsters [38] and shark jaws [39] (Figure 1). In each of these examples, the localised use of the material constituents and their interface arrangement is essential for their optimal performance. ...
Carbon fiber composites with increased fiber-to-matrix bonding are often susceptible to premature failure due to the creation of overly rigid interfaces. This paper investigates the use of electrochemically functionalised carbon fibers used in novel ‘hybrid interface’ arrangements to improve out-of-plane bending. An improvement of 103.6% in single fiber interfacial shear strength (IFSS) was able to improve out-of-plane strength by 33.6% for short beam shear laminates. However, by combining both functionalised and non-functionalised fibers in complex hybrid interface arrangements such as nature inspired turtle-shell interfaces and circular patterns, mechanical performance was improved significantly. A 170.9% increase to out-of-plane strength was observed using a turtle-shell arrangement which correlated to an 8.7% reduction in composite weight as compared to control fibers.
... On the other hand, the presence of calcium phosphate, notably in the form of amorphous calcium phosphate (ACP) and carbonate apatite (CAP), in addition to calcium carbonate (CaCO 3 ) , as amorphous calcium carbonate (ACC) and calcite, is common in the exoskeleton of decapods and isopods (Becker et al., 2005;Boßelmann et al., 2007;Fabritius et al., 2012;Greenaway, 1985;Grunenfelder et al., 2014;Hild et al., 2008Hild et al., , 2009Kunkel, 2013;Levi-Kalisman et al., 2002;Luquet, 2012;Neues et al., 2007;Soejoko and Tjia, 2003;Vijayan and Diwan, 1996). Calcium phosphate has also been evidenced in the cuticle of peculiar limbs of stomatopods: the smashing limb of the mantis shrimp, Gonodactylus chiragra (Currey et al., 1982) and the hammer-like dactyl club of the peacock mantis shrimp, Odontodactylus scyllarus (Weaver et al., 2012). ...
... This last process occurs by precipitation of calcium carbonate and, to a lesser extent, calcium phosphate as amorphous calcium phosphate (ACP) or carbonate apatite in a threedimensional network of organic matter synthesized by hypodermal cells. This has been mainly studied in decapods (Soejoko & Tjia, 2003; Dillaman et al., 2005; Romano et al., 2007; Kunkel & Jercinovic, 2013; Grunenfelder et al., 2014) and isopods (Becker et al., 2005; Neues et al., 2007). Calcium ions are more or less available in the aquatic biotopes and branchial calcium uptake constitutes the major cuticular contribution of calcium ions for aquatic species in postmolt. ...
The crayfish Cherax quadricarinatus stores calcium ions, easily mobilizable after molting, for
calcifying parts of the new exoskeleton. They are chiefly stored as amorphous calcium carbonate (ACC) during
each premolt in a pair of gastroliths synthesized in the stomach wall. How calcium carbonate is stabilized in the
amorphous state in such a biocomposite remains speculative. The knowledge of the microstructure at the
nanometer level obtained by field emission scanning electron microscopy and atomic force microscopy
combined with scanning electron microscopy energy-dispersive X-ray spectroscopy, micro-Raman and X-ray
absorption near edge structure spectroscopy gave relevant information on the elaboration of such an
ACC-stabilized biomineral. We observed nanogranules distributed along chitin-protein fibers and the
aggregation of granules in thin layers. AFM confirmed the nanolevel structure, showing granules probably
surrounded by an organic layer and also revealing a second level of aggregation as described for other crystalline
biominerals. Raman analyses showed the presence of ACC, amorphous calcium phosphate, and calcite. Elemental
analyses confirmed the presence of elements like Fe, Na, Mg, P, and S. P and S are heterogeneously distributed.
P is present in both the mineral and organic phases of gastroliths. S seems present as sulfate (probably as sulfated
sugars), sulfonate, sulfite, and sulfoxide groups and, in a lesser extent, as sulfur-containing amino acids.
... This last process occurs by precipitation of calcium carbonate and, to a lesser extent, calcium phosphate as amorphous calcium phosphate (ACP) or carbonate apatite in a threedimensional network of organic matter synthesized by hypodermal cells. This has been mainly studied in decapods (Soejoko & Tjia, 2003;Dillaman et al., 2005;Romano et al., 2007;Kunkel & Jercinovic, 2013;Grunenfelder et al., 2014) and isopods (Becker et al., 2005;Neues et al., 2007). Calcium ions are more or less available in the aquatic biotopes and branchial calcium uptake constitutes the major cuticular contribution of calcium ions for aquatic species in postmolt. ...
The crayfish
Cherax quadricarinatus
stores calcium ions, easily mobilizable after molting, for calcifying parts of the new exoskeleton. They are chiefly stored as amorphous calcium carbonate (ACC) during each premolt in a pair of gastroliths synthesized in the stomach wall. How calcium carbonate is stabilized in the amorphous state in such a biocomposite remains speculative. The knowledge of the microstructure at the nanometer level obtained by field emission scanning electron microscopy and atomic force microscopy combined with scanning electron microscopy energy-dispersive X-ray spectroscopy, micro-Raman and X-ray absorption near edge structure spectroscopy gave relevant information on the elaboration of such an ACC-stabilized biomineral. We observed nanogranules distributed along chitin-protein fibers and the aggregation of granules in thin layers. AFM confirmed the nanolevel structure, showing granules probably surrounded by an organic layer and also revealing a second level of aggregation as described for other crystalline biominerals. Raman analyses showed the presence of ACC, amorphous calcium phosphate, and calcite. Elemental analyses confirmed the presence of elements like Fe, Na, Mg, P, and S. P and S are heterogeneously distributed. P is present in both the mineral and organic phases of gastroliths. S seems present as sulfate (probably as sulfated sugars), sulfonate, sulfite, and sulfoxide groups and, in a lesser extent, as sulfur-containing amino acids.
Capillary rise infiltration (CaRI) enables the fabrication of polymer nanocomposite films (PNCFs) with high nanoparticle loading (> 50 vol%). The process involves generating a bilayer of nanoparticle and polymer film, and thermally annealing the film above the glass transition temperature (Tg) of the polymer to induce polymer imbibition into the voids in the nanoparticle packing. Upon CaRI, polymer experiences strong physical confinement within the nanoparticle packing, which may lead to changes in the polymer properties and the infiltration dynamics, subsequently affecting the macroscopic PNCF structure and properties. As such, understanding polymer behavior under confinement is crucial to enable optimal process and nanocomposite design. In this work, we study the effect of physical confinement, polymer-nanoparticle interactions, and undersaturation on the polymer CaRI dynamics. We utilize in situ spectroscopic ellipsometry to determine the effective polymer viscosity based on the Lucas-Washburn analysis, and to determine the polymer Tg when confined in the nanoparticle packing. We observe increased polymer viscosity and Tg with confinement, until a threshold confinement ratio is reached. Furthermore, under extreme nanoconfinement, the polymer-nanoparticle interaction is negligible relative to the confinement effect. In undersaturated CaRI (UCaRI), such that a bilayer film with insufficient polymer to completely fill the void space in the nanoparticle packing is annealed, there is a two-stage filling process – a rapid capillary rise with a clear invading front, and a gradual polymer spreading likely via surface diffusion. As such, the UCaRI process enables the fabrication of nanoporous polymer-infiltrated nanoparticle films with uniform or gradient composition, depending on the annealing time and polymer volume fraction. These UCaRI films also have tunable optical and mechanical properties with polymer composition. Finally, we characterize the fracture toughness of UCaRI films based on a nanoindentation-based pillar splitting method. We show that confinement-induced polymer capillary bridges and chain bridging of nanoparticles to drastically toughen the UCaRI film, even upon infiltrating small amounts of polymer. Thus, this work provides insights to the processing-structure-property relationships of the CaRI process to generate functional nanocomposite films with high nanoparticle loadings.
The crustaceans constitute one of the oldest arthropod taxa, from which insects later evolved (Giribet et al., Nature 413:157–161, 2001; Regier et al., Nature 463:1079–U1098, 2010; Giribet and Edgecombe, Annu Rev Entomol 57:167–186, 2012). A typical feature that characterizes the Crustacea is their mineralized chitinous exoskeleton. The reinforcement of the chitinous exoskeleton with calcium salts and the formation of inorganic-organic composite materials by the crustaceans represent one of the oldest biomineralization mechanisms to have evolved in animals. The basic function of mineralization is to enhance the mechanical strength of the skeleton. When compared to other animals with mineralized skeletons, crustaceans face two distinct challenges inherent in the fact that their skeleton is external: first, the animal’s locomotion abilities must not be compromised by its mineralized exoskeleton, and second, the growth mode by periodic molting requires intensive mobilization of minerals during the resorption of the old cuticle and the rapid recalcification of the new cuticle. These two demands are among the prime determinants that govern the various calcification patterns in Crustacea. This review focuses on the mineralogical aspects of the crustacean exoskeleton with emphasis on the controllable parameters of the mineral phase properties, namely, the degree of mineralization, the degree of crystallization, the phosphate/carbonate ratio, and the involvement of proteins. It also explores potential biomimetic applications inspired by the crustacean exoskeleton against the background of similarities between crustaceans and vertebrates, namely, both groups are the only groups in the animal kingdom that combine advanced locomotion with jointed mineralized skeletons. In addition, many crustaceans have the ability of calcium phosphate mineralization, like vertebrates. These similarities provide unique opportunities to compare different evolutional solutions to similar functional challenges that, in turn, can inspire biomimetic approaches to the development of synthetic bio-composites for various skeleton-related medical applications.
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