Micromechanical properties and structural characterization of modern inarticulated brachiopod shells
Journal of Geophysical Research-Biogeosciences 112(G2): G02008
 We investigated micromechanical properties and ultrastructure of the shells of the modern brachiopod species Lingula anatina, Discinisca laevis, and Discradisca stella with scanning electron microscopy (SEM, EDX), transmission electron microscopy (TEM) and Vickers microhardness indentation analyses. The shells are composed of two distinct layers, an outer primary layer and an inner secondary layer. Except for the primary layer in Lingula anatina, which is composed entirely of organic matter, all other shell layers are laminated organic/inorganic composites. The organic matter is built of chitin fibers, which provide the matrix for the incorporation of calcium phosphate. Amorphous calcium phosphate in the outer, primary layer and crystalline apatite is deposited into the inner, secondary layer of the shell. Apatite crystallite sizes in the umbonal region of the shell are about 50 x 50 nm, while within the valves crystallite sizes are significantly smaller, averanging 10 x 25 nm. There is great variation in hardness values between shell layers and between the investigated brachiopod species. The microhardness of the investigated shells is significantly lower than that of inorganic hydroxyapatite. This is caused by the predominantly organic material component that in these shells is either developed as purely organic layers or as an organic fibrous matrix reinforced by crystallites. Our results show that this particular fiber composite material is very efficient for the protection and the support of the soft animal tissue. It lowers the probability of crack formation and effectively impedes crack propagation perpendicular to the shell by crack-deviation mechanisms. The high degree of mechanical stability and toughness is achieved by two design features. First, there is the fiber composite material which overcomes some detrimental and enhances some advantageous properties of the single constituents, that is the softness and flexibility of chitin and the hardness and brittleness of apatite. Second, there is a hierarchical structuring from the nanometer to a micrometer level. We could identify at least seven levels of hierarchy within the shells.