UDC 549.731.13.057 : 544.178

Ivanitskiy V.P. (1), Ponomarenko O.M. (1), Brik A.B. (1), Dudchenko N.O. (1), Polshin E.V. (2), Ovsienko V.V. (1), Red’ko Ya.V. (3)
(1) M.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of the NAS of Ukraine
34, Acad. Palladina Pr., Kyiv-142, Ukraine, 03680
(2) G.V. Kurdyumov Institute for Metal Physics of the NAS of Ukraine
36, Acad. Vernadsky Pr., Kyiv-142, Ukraine, 03680
(3) Kyiv National University of Technologies and Design
2, Nemirovicha-Danchenko Str., Kyiv-11, Ukraine, 01601
Mineralogical journal 2016, 38 (3): 39-46

Abstract: Kinetics of "aging" of magnetically ordered nanoparticles, synthesized by the method of hydrothermal precipitation in nitrogen atmosphere, during their storage at ambient conditions for 1817 days, was investigated by the methods of Mossbauer spectroscopy and magnetometry. Phase composition of freshly synthesized sample and its changes during the fixed terms of storage were determined. The main phase of the synthesized nanoparticles, with contribution to absorption of total Mossbauer spectra (MS) of 89 %, was magnetite — ferrimagnetic material and the main carrier of magnetism. The contributions of impurity phases components to MS of the sample are: maghemite — 4 %, goethite — 7 %. Saturation magnetization of initial sample with above mentioned phase ratio was 55 A · m2/kg. The analysis of MS of the samples, which were under the influence of environment during 1817 days, shows a decrease of magnetite contribution from 89 to 70 %, as well as increase of contributions of maghemite from 4 to 20 % and goethite from 7 to 12 %. Thus, "aging" of nanoparticles occurs as the process of phase transformations with time, which is accompanied by decreasing of magnetite concentration and increasing of maghemite and goethite concentrations in the sample. The increase of maghemite concentration may be explained by magnetite oxidation. The sources of magnetite oxidation could be oxidizers of the environment, excess of oxygen ions, hydroxyl groups of chemically bound water, which presence in nanoparticles could be associated with its synthesis by precipitation method and which could lead to disturbances of stoichiometry of ion configuration of mineral particles. Formation of goethite in nanoparticles composition is, probably, associated with intermediate stages of synthesis in the presence of aqueous solutions. Some increase of goethite concentration during storage of nanoparticles could be explained by transformation of coexisting magnetite and maghemite. Possibilities of such transformation and patterns of their realization in certain experimental conditions are described in the cited literature. The most significant changes of concentrations of phase components of nanoparticles occur during their storage up to 1360 days. After that, the processes of phase transformations get to saturation. Changes of the ratio of initial and final (after storage during 1817 days) samples lead to the decrease of saturation magnetisation of the sample to 41 А · m2/kg. Obtained results could be used for interpretation of phase transformations and evaluation of their intensity during long-term storage of finely dispersed iron ores, as well as for creation of methods of synthesis of magnetically ordered nanoparticles of iron oxides and hydroxides, which are analogues of biogenic magnetite.

Keywords: synthetic magnetically ordered nanoparticles, Mossbauer spectroscopy, saturation magnetization, phase transformation, magnetite, maghemite, goethite.


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