Semipermanently polarized
hydroxyapatite, named SP/HAp(w), is obtained
by applying a constant dc electric field of 1–10 kV/cm at 300–850
°C to the samples previously sintered in water vapor, while permanently
polarized hydroxyapatite, PP/HAp(a), is produced by applying a dc
electric field of 3 kV/cm at 1000 °C to the samples sintered
in air. SP/HAp(w) has been used for biomedical applications, while
PP/HAp(a) has been proved to be a valuable catalyst for N2 and CO2 fixation. In this work, structural differences
between SP/HAp(w) and PP/HAp(a) have been ascertained using Raman
microscopy, wide-angle X-ray diffraction, scanning electronic microscopy,
high-resolution transmission electron microscopy, and grazing incidence
X-ray diffraction. Results prove the existence of crystal distortion
in the form of amorphous calcium phosphate and β-tricalcium
phosphate (β-TCP) phases close to the surface because of the
atmosphere used in the sintering process. The existence of an amorphous
layer in the surface and the phase transition through β-TCP
of SP/HAp(w) are the structural factors responsible for the differences
with respect to PP/HAp(a). Moreover, a superstructure has been identified
in PP/HAp(a) samples, which could be another structural factor associated
with enhanced conductivity, permanent polarization, and catalytic
activity of this material.