Exotic FeII/FeIII Local Environments in the Hexagonal Channels of Hydroxyapatite.

In this fundamental solid-state chemistry study, two sample series were investigated in depth: iron(III)-doped hydroxyapatite (HA) compounds obtained from a co-sintering process of hematite and pure HA under air and iron(III)-doped HA compounds obtained from a co-sintering process from iron(II) acetate and pure HA under an argon atmosphere. X-ray diffraction, UV-visible, Fourier transform infrared, 1H and 31P NMR, electron paramagnetic resonance (EPR,) and Mössbauer spectroscopy methods were coupled to unravel the Fe valence states, the interactions with other anionic species (OH- and PO43-), and finally the complex local environments in hexagonal channels in both the series. In particular, we highlighted the associated mechanism to ensure electroneutrality with a focus on deprotonation versus calcium substitution. By diverging mechanisms, Fe3+ and Fe2+ ions were found to be located in different coordinated sites: 4(+1) coordinated site for Fe3+ and 2(+3) coordinated site for Fe2+ and clearly associated with very different Mössbauer and EPR signatures as various absorption bands (leading to different sample colors).

Understanding the effects of PBF process parameter interplay on Ti-6Al-4V surface properties.

Ti-6Al-4V is commonly used in orthopaedic implants, and fabrication techniques such as Powder Bed Fusion (PBF) are becoming increasingly popular for the net-shape production of such implants, as PBF allows for complex customisation and minimal material wastage. Present research into PBF fabricated Ti-6Al-4V focuses on new design strategies (e.g. designing pores, struts or lattices) or mechanical property optimisation through process parameter control-however, it is pertinent to examine the effects of altering PBF process parameters on properties relating to bioactivity. Herein, changes in Ti-6Al-4V microstructure, mechanical properties and surface characteristics were examined as a result of varying PBF process parameters, with a view to understanding how to tune Ti-6Al-4V bio-activity during the fabrication stage itself. The interplay between various PBF laser scan speeds and laser powers influenced Ti-6Al-4V hardness, porosity, roughness and corrosion resistance, in a manner not clearly described by the commonly used volumetric energy density (VED) design variable. Key findings indicate that the relationships between PBF process parameters and ultimate Ti-6Al-4V properties are not straightforward as expected, and that wide ranges of porosity (0.03 ± 0.01% to 32.59 ± 2.72%) and corrosion resistance can be achieved through relatively minor changes in process parameters used-indicating volumetric energy density is a poor predictor of PBF Ti-6Al-4V properties. While variations in electrochemical behaviour with respect to the process parameters used in the PBF fabrication of Ti-6Al-4V have previously been reported, this study presents data regarding important surface characteristics over a large process window, reflecting the full capabilities of current PBF machinery.