XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
30
I–12
New minerals as potential prototypes for advanced materials:
Raman investigation of hexagonal broken antiperovskite
with a modular structure derived from hatrurite
Evgeny Galuskin
1
1
Department of Geochemistry, Mineralogy and Petrography, Faculty of Earth Sciences, University of
Silesia, Będzińska 60, 41-200 Sosnowiec, Poland, e-mail: evgeny.galuskin@us.edu.pl
Minerals – natural solids, many times play the role of prototypes for creating of advanced
materials. Perovskite, CaTiO
3
, discovered more than 150 years ago, was an ancestor for engineering
of perovskite structure based materials, which have widespread applications from superconductors to
materials for immobilization of radioactive wastes [1]. In pyrometamorphic rocks of the Hatrurim
Complex (Israel, Palestinian Autonomy, Jordan), represented by natural high-temperature ceramics,
new minerals having structure of a broken (intercalated) hexagonal antiperovskite were recently
discovered. Antiperovskites (inverse perovskites) are inorganic compounds with a perovskite
structure but with cations replaced by anions. Structure of the new minerals are presented by a
modular structure derived from hatrurite of two types described by the next crystal chemical
formulas: AB
12
(TO
4
)
4
(TO
4
)
2
W
3
(structural type 3:1, nabimusiate group) and AB
6
(TO
4
)
2
(TO
4
)
2
W
(structural type 1:1, zadovite group), where A = Ba, K, Sr...; B = Ca, Na...; T = Si, P, V
5+
, S
6+
, Al...;
W
= O
2-
, F
-
.
The nabimusaite group combines nabimusaite KCa
12
(SiO
4
)
4
(SO
4
)
2
O
2
F [2], dargaite,
BaCa
12
(SiO
4
)
4
(SO
4
)
2
O
3
[3], and ariegilatite BaCa
12
(SiO
4
)
4
(PO
4
)
2
F
2
O [4]. The zadovite group units the
following
minerals
species:
zadovite
BaCa
6
[(SiO
4
)(PO
4
)](PO
4
)
2
F,
aradite
BaCa
6
[(SiO
4
)(VO
4
)](VO
4
)
2
F,
gazeevite
BaCa
6
(SiO
4
)
2
(SO
4
)
2
O,
strecherite
BaCa
6
(SiO
4
)
2
[(PO
4
)(CO
3
)]F [4–6]. Antiperovskite single
{[WB
6
](TO
4
)
2
} and triple {[W
3
B
12
](TO
4
)
4
} layers intercalate with single glaserite-like A(TO
4
)
2
layers
in minerals of the zadovite and nabimusaite groups, respectively [2, 4, 6]. Minerals of the nabimusaite
and zadovite groups form micron-sized grains and they are represented by solid solutions with diverse
combinations of tetrahedral cations, that is responsible for Raman spectroscopy to be the one from the
main methods of these mineral investigations. Using of Raman spectroscopy at the stages of
searching and discovery of potentially new minerals will be considered in this report. Also results of
Raman study of approved by CNMNC IMA minerals with antiperovskite structure and solid solutions
between them (zadovite-aradite, nabimusaite-dargaite, dargaite-ariegilatite and etc.) will be discussed.
Raman spectroscopy is an irreplaceable method for study of mineral phases containing chemical
elements unmeasurable by means of microprobe technics (EDS/WDS), that will be shown on the
examples of stracherite and potentially new minerals – OH- and CO
3
-analogs of ariegilatite and also
antiperovskite minerals with mixed structure. Questions of using of nabimusaite and zadovite group
minerals as prototypes for creation of new advanced materials will be review. Structure of broken
hexagonal antiperovskites is a combination of hatrurite- and glaserite-like layers. Hatrurite, Ca
3
SiO
5
,
is an analogue of synthetic allite, the main component of cement clinkers. P
5+
, V
5+
, S
6+
, Al, Si... may
be in tetrahedral sites, and K, Ba, Sr, Na... – in octahedral sites in glaserite-like layers, what allow to
synthesize different predetermined-properties materials.
Keywords: broken antiperovskite; new minerals, nabimusaite, zadovite, aradite, Raman spectroscopy
References
[1] R. Mitchell, M.D. Welch, A.R. Chakhmouradian, Mineral. Mag. 81 (2017) in press.
[2] E.V.Galuskin, F. Gfeller, T. Armbruster, I.O. Galuskina, Ye. Vapnik, M. Murashko, R. Wodyka, P.
Dzierżanowski, Mineral. Mag. 79 (2015) 1061.
[3] F. Gfeller, I.O. Galuskina, E.V. Galuskin, T. Armbruster, Y. Vapnik, M. Dulski, M. Gardocki, L. Jeżak, M.
Murashko, Mineral. Mag. 79 (2015) 1859.
[4] E.V. Galuskin, B. Krüger, I.O. Galuskina, H. Krüger, Y. Vapnik, J.A. Wojdyla, M. Murashko, Mineral. Mag.
81 (2017) in press.
[5] E.V.Galuskin, F. Gfeller, I.O. Galuskina, A. Pakhomova, T. Armbruster, Y. Vapnik, R. Włodyka, P.
Dzierżanowski, M. Murashko, Mineral. Mag. 79 (2015) 1073.
[6] E.V. Galuskin, F. Gfeller, I.O. Galuskina, T. Armbruster, A. Krzątała, Ye. Vapnik, J. Kusz, M. Dulski, M.
Gardocki, A.G. Gurbanov, P. Dzierżanowski, Mineral. Mag. 81 (2017) in press.
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