Structure of denisovite, a fibrous nanocrystalline polytypic disordered 'very complex' silicate

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Marco E. Ciriotti
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Iscritto il: ven 25 giu, 2004 11:31
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Structure of denisovite, a fibrous nanocrystalline polytypic disordered 'very complex' silicate

Messaggio da Marco E. Ciriotti » mar 02 mag, 2017 13:20

Referenza:
▪ Rozhdestvenskaya, I.V., Mugnaioli, E., Schowalter, M., Schmidt, M.U., Czank, M., Depmeier, W., Rosenauer, A. (2017): The structure of denisovite, a fibrous nanocrystalline polytypic disordered `very complex' silicate, studied by a synergistic multi-disciplinary approach employing methods of electron crystallography and X-ray powder diffraction. IUCrJ, 4, 223-242.

Abstract:
Denisovite is a rare mineral occurring as fibres typically 200–500 nm in diameter, always characterized by pervasive disorder. Combining X-ray powder diffraction, high-angle annular dark-field scanning transmission electron microscopy imaging and electron diffraction tomography, it was possible to determine the denisovite structure and describe its disorder and polytypism by order–disorder theory. The denisovite structure ranks among the top 1% of the most complex mineral structures known to date.

NdR: Chapeau! Un lavoro di eccellenza.
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Marco E. Ciriotti

«Things are interesting only in so far as they relate themselves to other things»

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Marco E. Ciriotti
Messaggi: 24371
Iscritto il: ven 25 giu, 2004 11:31
Località: via San Pietro, 55 I-10073 Devesi/Cirié TO - Italy
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Re: Structure of denisovite, a fibrous nanocrystalline polytypic disordered 'very complex' silicate

Messaggio da Marco E. Ciriotti » mar 12 dic, 2017 11:25

Una delle strutture più complesse in assoluto.
La stessa "very complex" struttura ha la charoite che si rinviene nella stessa località.

Un abstract più completo è qui di seguito:

Denisovite is a rare mineral occurring as aggregates of fibres typically 200–500 nm diameter. It was confirmed as a new mineral in 1984, but important facts about its chemical formula, lattice parameters, symmetry and structure have remained incompletely known since then. Recently obtained results from studies using microprobe analysis, X-ray powder diffraction (XRPD), electron crystallography, modelling and Rietveld refinement will be reported. The electron crystallography methods include transmission electron microscopy (TEM), selected-area electron diffraction (SAED), high-angle annular darkfield imaging (HAADF), high-resolution transmission electron microscopy (HRTEM), precession electron diffraction (PED) and electron diffraction tomography (EDT). A structural model of denisovite was developed from HAADF images and later completed on the basis of quasi-kinematic EDT data by ab initio structure solution using direct methods and least-squares refinement. The model was confirmed by Rietveld refinement. The lattice parameters are a = 31.024 (1), b = 19.554 (1) and c = 7.1441 (5) A°, beta = 95.99 (3), V = 4310.1 (5) A°3 and space group P12/a1. The structure consists of three topologically distinct dreier silicate chains, viz. two xonotlite-like dreier double chains, [Si6O17]10, and a tubular loop-branched dreier triple chain, [Si12O30]12.
The silicate chains occur between three walls of edge-sharing (Ca,Na) octahedra. The chains of silicate tetrahedra and the octahedra walls extend parallel to the z axis and form a layer parallel to (100). Water molecules and K+ cations are located at the centre of the tubular silicate chain. The latter also occupy positions close to the centres of eight-membered rings in the silicate chains. The silicate chains are geometrically constrained by neighbouring octahedra walls and present an ambiguity with respect to their z position along these walls, with displacements between neighbouring layers being either z = c/4 or c/4. Such behaviour is typical for polytypic sequences and leads to disorder along [100]. In fact, the diffraction pattern does not show any sharp reflections with l odd, but continuous diffuse streaks parallel to a* instead. Only reflections with l even are sharp. The diffuse scattering is caused by (100) nanolamellae separated by stacking faults and twin boundaries. The structure can be described according to the order–disorder (OD) theory as a stacking of layers parallel to (100).
Marco E. Ciriotti

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