Hydrothermal Preparation and Characterization of Zn, Si, Mg, Fe Doped Hydroxyapatite

doi:10.15541/jim20200664

Abstract

Abstract:

Doping of trace elements is an effective way to endow hydroxyapatite with more biological functions. But the behaviors of different element doping remained to be further revealed. Here, nine kinds of hydroxyapatite particles containing zinc, silicon, magnesium, iron, manganese, copper, strontium, selenium, and cobalt, respectively, were prepared by parallel hydrothermal synthesis, and their physicochemical properties were studied. The results show that the morphology and crystal growth direction of hydroxyapatite particles are significantly changed, while the phase composition is maintained. The peak intensity of (211) and (112) plane diffraction peaks decreased, accompanied by decreased crystallinity. Analysis results show that the actual doping efficiency obeys the tendency of manganese > zinc > magnesium > iron (trivalent) > strontium > cobalt > copper > selenium > silicon. Among these elements, doping amounts of Mn, Zn and Mg are higher, because their ion radii are closed to that of Ca ²⁺. The low doping efficiency of copper is caused by its complexation with ammonia in synthetic solution, while silicon and selenium are caused by different geometry and charge of SiO₃^2-, SeO₃^2- from that of PO₄^3-. This study reveals the reasonable relationship between doping behavior and ion characteristics, providing a useful reference for design and development of functionalized hydroxyapatite.

Key words: hydroxyapatite, element doping, hydrothermal synthesis, doping behavior

CLC Number:

R318

SONG Keke, HUANG Hao, LU Mengjie, YANG Anchun, WENG Jie, DUAN Ke. Hydrothermal Preparation and Characterization of Zn, Si, Mg, Fe Doped Hydroxyapatite[J]. Journal of Inorganic Materials, 2021, 36(10): 1091-1096.

Figures/Tables 7

Fig. 1 SEM images of hydroxyapatite samples doped by different elements at 1%, 3% and 5% doping amount (a1-a3) Zn-HA; (b1-b3) Si-HA; (c1-c3) Mg-HA; (d1-d3) Fe-HA; (e1- e3) Mn-HA; (f1-f3) Sr-HA; (g1-g3) Se-HA; (h1-h3) Co-HA; (i1-i3) Cu-HA; (j1) HA

Fig. 2 XRD patterns from 2θ=20° to 70° of hydroxyapatite samples with 5% doping amount

Table 1 Crystallinity and lattice parameters of 5% element doped samples (1 Å =0.1 nm)

Sample	Crystallinity/%	a/Å	b/Å	c/Å
HA	97.24	9.44	9.44	6.89
5%Zn-HA	82.60	9.45	9.45	6.88
5%Si-HA	95.19	9.43	9.43	6.88
5%Mg-HA	85.75	9.45	9.45	6.88
5%Fe-HA	95.40	9.44	9.44	6.89
5%Mn-HA	94.01	9.42	9.42	6.87
5%Sr-HA	85.37	9.44	9.44	6.90
5%Se-HA	92.85	9.43	9.43	6.88
5%Co-HA	92.31	9.43	9.43	6.88
5%Cu-HA	91.15	9.45	9.45	6.88

Fig. 3 FT-IR spectra of functional groups of hydroxyapatites doped by different elements at 5% doping amount

Fig. 4 Actual doping efficiency of hydroxyapatite doped by different element at 5% doping amount

Table 2 Ion (atom) radius size of doped elements

Ion	Radius dimension/nm
Ca²⁺	0.099
Sr²⁺	0.113
Mn²⁺	0.080
Co²⁺	0.074
Zn²⁺	0.074
Cu²⁺	0.072
Mg²⁺	0.065
Fe³⁺	0.064

Fig. 5 Spatial configurations of phosphate ion and n-silicate ion

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