| 1. |
- Bosi, Ferdinando, et al.
(författare)
-
Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4
- 2016
-
Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 101, s. 580-586
-
Tidskriftsartikel (refereegranskat)abstract
- Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X‑ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V3+1.48V4+0.26)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4.The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 Å), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 Å). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel.An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment.
|
|
| 2. |
- D'Ippolito, Veronica, et al.
(författare)
-
Crystallographic and spectroscopic characterisation of a natural Zn-rich spinel approaching the endmember gahnite (ZnAl2O4) composition
- 2013
-
Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 77, s. 2941-2953
-
Tidskriftsartikel (refereegranskat)abstract
- The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ∼94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined asT–O 1.9485(6) Å andM–O 1.9137(3) Å. Crystal chemical analysis resulted in the empirical structural formulaT(Zn0.94Fe2+0.03Al0.03)M(Al1.96Fe2+0.03Fe3+0.01)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinatedTandMsites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Egmode at 420.6 cm–1and the T2gmodes at 510 cm–1and 661 cm–1, due to vibrations in the AlO6octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000 29000 cm–1show a dominant absorption band at ∼5000 cm–1which is caused by spin-allowed electronicd–dtransitions in Fe2+located at theTsites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions inTFe2+and toMFe2+↔MFe3+intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+and Fe3+.
|
|
| 3. |
|
|
| 4. |
|
|
