Structural study of the apatite Nd8Sr2Si6O26 by Laue neutron diffraction and single-crystal Raman spectroscopy.

A single-crystal structure determination of Nd8Sr2Si6O26 apatite, a prototype intermediate-temperature electrolyte for solid oxide fuel cells grown by the floating-zone method, was completed using the combination of Laue neutron diffraction and Raman spectroscopy. While neutron diffraction was in good agreement with P63/m symmetry, the possibility of P63 could not be convincingly excluded. This ambiguity was removed by the collection of orientation-dependent Raman spectra that could only be consistent with P63/m. The composition of Nd8Sr2Si6O26 was independently verified by powder X-ray diffraction in combination with electron probe microanalysis, with the latter confirming a homogeneous distribution of Sr and the absence of chemical zonation commonly observed in apatites. This comprehensive crystallochemical description of Nd8Sr2Si6O26 provides a baseline to quantify the efficacy of cation vacancies, oxygen superstoichiometry, and symmetry modification for promoting oxygen-ion mobility.

Textured fluorapatite bonded to calcium sulphate strengthen stomatopod raptorial appendages.

Stomatopods are shallow-water crustaceans that employ powerful dactyl appendages to hunt their prey. Deployed at high velocities, these hammer-like clubs or spear-like devices are able to inflict substantial impact forces. Here we demonstrate that dactyl impact surfaces consist of a finely-tuned mineral gradient, with fluorapatite substituting amorphous apatite towards the outer surface. Raman spectroscopy measurements show that calcium sulphate, previously not reported in mechanically active biotools, is co-localized with fluorapatite. Ab initio computations suggest that fluorapatite/calcium sulphate interfaces provide binding stability and promote the disordered-to-ordered transition of fluorapatite. Nanomechanical measurements show that fluorapatite crystalline orientation correlates with an anisotropic stiffness response and indicate significant differences in the fracture tolerance between the two types of appendages. Our findings shed new light on the crystallochemical and microstructural strategies allowing these intriguing biotools to optimize impact forces, providing physicochemical information that could be translated towards the synthesis of impact-resistant functional materials and coatings.