The Structure Features of Synthetic Apatites with REE Impurities by Data of Spectroscopy and X-Ray Analysis Methods: I. Hydroxylapatites
UDC 548.32 : 549.753.1 : 546.650 : 543.429.23
https://doi.org/10.15407/mineraljournal.37.04.021
E.А. Kalinichenko (1), А.B. Brik (1), А.М. Nikolaev (2), А.М. Kalinichenko (1), О.V. Frank-Kamenetskaya (2), О.V. Dubok (3), N.N. Bagmut (1), М.А. Kuz’mina (2), I.Е. Kolesnikov (2)
(1) M.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of the NAS of Ukraine
34, Acad. Palladina Pr., Kyiv-142, Ukraine, 03680
E-mail: kalinichenko@igmr.gov.ua, abrik@igmof.gov.ua
(2) Federal State Budgetary Educational "Saint Petersburg State University"
137/9, Universitetskaya Emb., Saint Petersburg, Russia, 199034
E-mail: ofrank-kam@mail.ru; mak_5262@mail.ru
(3) I.N. Frantsevich Institute for Problems of Materials Science of the NAS of Ukraine
3, Krzhizhanovsky Str., Kyiv-142, Ukraine, 03680
E-mail: dubok@mail.ru
The Structure Features of Synthetic Apatites with REE Impurities by Data of Spectroscopy and X-Ray Analysis Methods: I. Hydroxylapatites
Language: Russian
Mineralogical journal 2015, 37 (4): 21-35
Abstract: The methods of X-ray analysis, infrared spectroscopy, nuclear magnetic resonance (NMR), electronic paramagnetic resonance, X-ray spectroscopy microprobe analysis and luminescence spectroscopy have been applied to investigate the synthesized hydroxylapatites (HA) doped by rare-earth elements (REE): Y, La, Ce, Pr, Nd, Eu, Gd, Dy, Ho and Er. Apatites have been synthesized by precipitation under conditions close to those at (Т, рН) of natural biological synthesis and initial ratios of elements (Ca, REE) : P = 2 : 1 and REE : Ca = 0.05. As established, REE 3+ ions substitute Ca2+ ions in all synthesized apatites with the ratio REE/(Ca + REE) = 5—8 at. %. Higher substitution degrees are observed for Pr, Dy, Er and Ho. Nd has been accommodated in Ca1 sites, other REE, mainly — in Са2 sites. All synthesized samples contain water molecules H2Ostr (less than 1 wt. %) fixed in structure in the REE neighboring. The intensity ratios of the two components in the 31Р MAS NMR spectra of Ce-, Pr-, Eu- and Gd-HA are assumed to represent the occupancies of the Ca1 and Ca2 sites by REE (φLn = Ln2/Ln1). The REE content in the Ca2 site decreases with the increase of REE atomic number: φLn ≈ 30 (Ce), 20 (Pr), 10 (Eu) and 6 (Gd). It is assumed that the H2Ostr molecule content can be used as a criterion of natural apatites formation at low temperatures and high water activity. It is shown that the experimental results, obtained by different methods, substantially complement each other and allow establishing more exactly the crystallochemical features of REEapatites.
Keywords: apatite, REE, isomorphism, nuclear magnetic resonance, infrared spectroscopy, X-ray diffraction analysis.
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