Multiscale structure of nacre biomaterial: Thermomechanical behavior and wear processes.

Sheet nacre is a hybrid biocomposite with a multiscale structure, including nanograins of CaCO3 (97% wt% - 40 nm in size) and two organic matrices: (i) the interlamellar mainly composed of ß-chitin and proteins, and (ii) the intracrystalline composed by silk-fibroin-like proteins. This material is currently contemplated for the manufacture of small prostheses (e.g., rachis and dorsal vertebra prostheses) which are subjected to micro-slip or fretting motion. In this work, the tribological behavior of nacre is studied by varying the frictional dissipated power from few nW to several hundred mW, in order to assess the various responses of the different nacre's components, independently. Results reveal various dissipative mechanisms vs. dissipated frictional power: organic thin film lubrication, tablet's elastoplastic deformations, stick-slip phenomenon and/or multiscale wear processes, including various thermo-mechanical processes (i.e., mineral phase transformation, organics melting and friction-induced nanoshocks process on a large range). All these mechanisms are controlled by the multiscale and anisotropy of its structure - and especially by its both matrices and respective orientation vs. the sliding direction.

Multiscale structure of sheet nacre.

This work was conducted on Pinctada maxima nacre (mother of pearl) in order to understand its multiscale ordering and the role of the organic matrix in its structure. Intermittent-contact atomic force microscopy with phase detection imaging reveals a nanostructure within the tablet. A continuous organic framework divides each tablet into nanograins. Their shape is supposed to be flat with a mean extension of 45nm. TEM performed in the darkfield mode evidences that at least part of the intracrystalline matrix is crystallized and responds like a 'single crystal'. The tablet is a 'hybrid composite'. The organic matrix is continuous. The mineral phase is thus finely divided still behaving as a single crystal. It is proposed that each tablet results from the coherent aggregation of nanograins keeping strictly the same crystallographic orientation thanks to a hetero-epitaxy mechanism. Finally, high-resolution TEM performed on bridges from one tablet to the next, in the overlying row, did not permit to evidence a mineral lattice but crystallized organic bridges. The same organic bridges were evidenced by SEM in the interlaminar sequence.