Lower hardness than strength: The auxetic composite microstructure of limpet tooth.

The limpet tooth is widely recognized as nature's strongest material, with reported strength values up to 6.5 GPa. Recently, microscale auxeticity has been discovered in the leading part of the tooth, providing a possible explanation for this extreme strength. Utilizing micromechanical experiments, we find hardness values in nanoindentation that are lower than the respective strength observed in micropillar compression tests. Using micromechanical modeling, we show that this unique behavior is a result of local tensile strains during indentation, originating from the microscale auxeticity. As the limpet tooth lacks ductility, these tensile strains lead to microdamage in the auxetic regions of the microstructure. Consequently, indentation with a sharp indenter always probes a damaged version of the material, explaining the lower hardness and modulus values gained from nanoindentation. Micropillar tests were found to be mostly insensitive to such microdamage due to the lower applied strain and are therefore the suggested method for characterizing auxetic nanocomposites. STATEMENT OF SIGNIFICANCE: This work explores the micromechanical properties of limpet teeth, nature's strongest biomaterial, using micropillar compression testing and nanoindentation. The limpet tooth microstructure consists of ceramic nanorods embedded in a matrix of amorphous SiO2 and arranged in a pattern that leads to local auxetic behavior. We report lower values for nanoindentation hardness than for compressive strength, a unique behavior usually not achievable in conventional materials. Utilizing micromechanical finite element simulations, we identify the reason for this behavior to be microdamage formation resultant of the auxetic behavior, sharp indenter tip and lack of ductility of the limpet tooth microstructure. This formation of microdamage is not expected in micropillar compression tests due to lower locally imposed strain.

Limpet teeth microstructure unites auxeticity with extreme strength and high stiffness.

Materials displaying negative Poisson's ratio, referred to as auxeticity, have been found in nature and created in engineering through various structural mechanisms. However, uniting auxeticity with high strength and high stiffness has been challenging. Here, combining in situ nanomechanical testing with microstructure-based modeling, we show that the leading part of limpet teeth successfully achieves this combination of properties through a unique microstructure consisting of an amorphous hydrated silica matrix embedded with bundles of single-crystal iron oxide hydroxide nanorods arranged in a pseudo-cholesteric pattern. During deformation, this microstructure allows local coordinated displacement and rotation of the nanorods, enabling auxetic behavior while maintaining one of the highest strengths among natural materials. These findings lay a foundation for designing biomimetic auxetic materials with extreme strength and high stiffness.

Orientation-dependent micromechanical behavior of nacre: In situ TEM experiments and finite element simulations.

Nacre's superior mechanical properties and failure behavior are strongly orientation-dependent due to its brick-and-mortar microstructure. In this work, the anisotropic microscopic deformation and the resulting macroscopic mechanical properties are evaluated under different loading conditions. Our in situ transmission electron microscopy deformation experiments and finite element simulations reveal that nacre possesses enhanced indentation resistance along the direction normal to the tablets through delocalization of indentation-induced deformation by taking advantage of its layered structure. In addition, nacre's ability to recover from large deformations is observed. We study the strong loading direction dependence of nacre's macroscopic mechanical properties and elucidate the underlying microscopic deformation patterns in the tablets and the soft matrix. Particularly, its performance along the transverse direction is optimized to withstand the loading conditions in nature. We show the importance of the vertical matrix for the initial stiffness and fracture toughness of the composite. These findings provide guidelines for designing nacre-inspired artificial composites with enhanced mechanical properties. STATEMENT OF SIGNIFICANCE: Nacre is widely recognized as an excellent structural model for designing bio-inspired tough and strong artificial composites. Due to its brick-and-mortar microstructure, it exhibits loading direction-dependent mechanical behavior. In this contribution, we investigate the macroscopic mechanical properties and microscopic deformation behavior of nacre under different loading conditions by means of in situ TEM deformation tests and FE simulations. It is found that effective elastic moduli and microscopic deformation strongly depend on the loading direction. The organic matrix is highly deformable. The indentation resistance along the direction normal to tablets is enhanced via deformation delocalization. Our quantitative and qualitative results provide guidelines on optimizing the mechanical properties of nacre-inspired novel composites.

Hierarchical Microstructure of Tooth Enameloid in Two Lamniform Shark Species, Carcharias taurus and Isurus oxyrinchus.

Shark tooth enameloid is a hard tissue made up of nanoscale fluorapatite crystallites arranged in a unique hierarchical pattern. This microstructural design results in a macroscopic material that is stiff, strong, and tough, despite consisting almost completely of brittle mineral. In this contribution, we characterize and compare the enameloid microstructure of two modern lamniform sharks, Isurus oxyrinchus (shortfin mako shark) and Carcharias taurus (spotted ragged-tooth shark), based on scanning electron microscopy images. The hierarchical microstructure of shark enameloid is discussed in comparison with amniote enamel. Striking similarities in the microstructures of the two hard tissues are found. Identical structural motifs have developed on different levels of the hierarchy in response to similar biomechanical requirements in enameloid and enamel. Analyzing these structural patterns allows the identification of general microstructural design principles and their biomechanical function, thus paving the way for the design of bioinspired composite materials with superior properties such as high strength combined with high fracture resistance.

Nature's design solutions in dental enamel: Uniting high strength and extreme damage resistance.

The most important demand of today's high-performance materials is to unite high strength with extreme fracture toughness. The combination of withstanding large forces (strength) and resistance to fracture (toughness), especially preventing catastrophic material failure by cracking, is of utmost importance when it comes to structural applications of these materials. However, these two properties are commonly found to be mutually exclusive: strong materials are brittle and tough materials are soft. In dental enamel, nature has combined both properties with outstanding success - despite a limited number of available constituents. Made up of brittle mineral crystals arranged in a sophisticated hierarchical microstructure, enamel exhibits high stiffness and excellent toughness. Different species exhibit a variety of structural adaptations on varying scales in their dental enamel which optimise not only fracture toughness, but also hardness and abrasion behaviour. Nature's materials still outperform their synthetic counterparts due to these complex structure-property relationships that are not yet fully understood. By analysing structure variations and the underlying mechanical mechanisms systematically, design principles which are the key for the development of advanced synthetic materials uniting high strength and toughness can be formulated. STATEMENT OF SIGNIFICANCE: Dental enamel is a hard protective tissue that combines high strength with an exceptional resistance to catastrophic fracture, properties that in classical materials are commonly found to be mutually exclusive. The biological material is able to outperform its synthetic counterparts due to a sophisticated hierarchical microstructure. Between different species, microstructural adaptations can vary significantly. In this contribution, the different types of dental enamel present in different species are reviewed and connections between microstructure and (mechanical) properties are drawn. By consolidating available information for various species and reviewing it from a materials science point of view, design principles for the development of advanced biomimetic materials uniting high strength and toughness can be formulated.