The Study of Crystal Structure on Grossular–Andradite Solid Solution

The effects of Al3+–Fe3+ substitution on 10 synthesized garnet samples along the grossular–andradite binary solid solution were investigated using both powder and single-crystal X-ray diffraction. Results showed that cell volume increased with andradite content. Small negative excess volume was observed in the Al-rich samples. By measuring the bond length, polyhedral volume, octahedral distortion parameter (σ), and tetrahedral rotation angle (α), we determined that the distortion occurred on the dodecahedral site. The width of the diffraction peaks was obviously related to the composition of the solid solution. Full width at half maximum of diffraction peaks was used to calculate the microstrain, which may have a relationship with enthalpy of mixing.

Features of Optical Anisotropy of Terbium Iron Garnet

Rare earth iron garnets with narrow ferromagnetic resonance linewidths, very low hysteresis losses, and excellent dielectric properties have been widely applied in microwave devices in a wide range of frequencies (1100 GHz), magnetooptical transducers and typically employed as magnetic recording media [1-1. The rare earth iron garnets which can be described by chemical unit formulaRE3Fe5O12belong to cubic system with space groupIa3̄d, whose cell contains eightRE3Fe5O12molecules and crystal lattice contains three crystallographic sites, dodecahedral site 24c{RE3+}, octahedral site 16a[Fe3+] and tetrahedral site 24d(Fe3+). The garnet in fact does not allow distortion to lower symmetry owing to its non-efficiently packed structure, which makes iron garnet structure become unstable with increasing rare earth ionic radius.

THE OH COMPONENTS IN GARNETS FROM DIFFERENTGEOLOGICAL ENVIRONMENTS: P-T AND BULK COMPOSITION CONSTRAINTS

Metamorphic garnet from the Anápolis-Itauçu Complex (AIC), central Brazil, were investigated by electron microprobe analyses and Mössbauer spectroscopy, in order to contribute on their geological history. The data were further extended by magmatic samples from complex and simple pegmatites, as reported by Eeckhout et al. (2002). Three clear chemical tendencies within garnets from AIC rocks were revealed. From Mössbauer spectroscopy data it is obvious that ferrous iron is present at dodecahedral site. Very small amounts of ferric iron at octahedral site of garnet structure are additionally present in garnets from sample of ultra-high temperature (UHT) granulites from AIC, implying slightly oxidizing conditions during this metamorphicevent. In addition, a higher degree of structural disorder has been discerned in these samples.Keywords: Garnet, petrogenetic indicator, hydroxyl, Mössbauer spectroscopy.

Systematic ab initio study of the compressibility of silicate garnets

The structural properties of the silicate garnets andradite, Ca3Fe2Si3O12, uvarovite, Ca3Cr2Si3O12, knorringite, Mg3Cr2Si3O12, goldmanite, Ca3V2Si3O12, blythite, Mn^{2+}_3Mn^{3+}_2Si3O12, skiagite, Fe^{2+}_3Fe^{3+}_2Si3O12, calderite, Mn^{2+}_3Fe^{3+}_2Si3O12, and khoharite, Mg3Fe^{3+}_2Si3O12, have been investigated with a quantum-mechanical model as a function of applied pressure. The study has been performed with the density functional theory code CASTEP, which uses pseudopotentials and a plane-wave basis set. All structural parameters have been optimized. The calculated static geometries (cell parameters, internal coordinates of atoms and bond lengths), bulk moduli and their pressure derivatives are in good agreement with the experimental data available. Predictions are made for those cases where no experimental data have been reported. The data clearly indicate that the elastic properties of all silicate garnets are dominated by the compressibility of the dodecahedral site. The compression mechanism is found to be based on a bending of the angle between the centers of the SiO4 tetrahedra and the adjacent octahedra, as in the aluminosilicate garnets. An analysis of the relationship between ionic radii of the cations and the compressibility of silicate garnets is presented.

57Fe-Mössbauer investigation on garnets from the Ivrea-Verbano Zone

A Mössbauer investigation has been carried out on garnets from the Ivrea-Verbano zone and the results are compared with those obtained on the same samples by X-ray absorption spectroscopy (XAS). The problem addressed is the precise structural characterisation of the local environment of iron in garnets with Fe/Ca ratio variable between ∼3.0 and ∼18.0. Ferric iron is octahedrally coordinated and ferrous iron is in the dodecahedral site in all the samples. Mössbauer results are in agreement with those obtained by XAS and show that, at least in the compositional range of the garnets examined (0.1-0.5 calcium atoms p.f.u.), the iron environment is not significantly modified by the larger calcium cations sharing the same dodecahedral site. It is confirmed that the Mössbauer technique is more sensitive than XAS in detecting low percentages of iron, especially when the cation is present in more than one oxidation state and coordination number.

X-ray absorption study at the Fe K-edge of garnets from the Ivrea-Verbano zone

K-edge X-ray absorption spectra of Fe in garnet samples from the Ivrea-Verbano zone were collected using synchrotron radiation. From XANES analysis, the prevalent oxidation state of Fe has been determined as 2+ in all studied samples. Coordination numbers and Fe-O bond lengths derived from the EXAFS analysis are compatible with a dodecahedral environment of Fe atoms and seem to be nearly independent of the variable Fe/Ca ratio of the cations sharing the dodecahedral site in these garnets. This suggests that, since at least up to 0.5 Ca atoms p.f.u, no sensible deformation of the dodecahedron geometry is sensed by the Fe cations, iron might strongly compete with Ca atoms in controlling the entry of rare earth elements in the dodecahedral site of garnets falling within this compositional range. Comparison of the EXAFS results with the data from single crystal X-ray diffraction structure refinements indicates a first shell neighbour distance accuracy of ±0.02 Å, using theoretical EXAFS phases and amplitudes. The Debye-Waller factors derived from the EXAFS analysis indicate a higher degree of disorder on the four longer Fe-O bond distances, in comparsion with the other four shorter distances of the height-coordinated cation; this could be related to the nonrigid polyhedral behaviour of the dodecahedral site.

Infrared spectra of synthetic almandine–grossular and almandine–pyrope garnet solid solutions: evidence for equivalent site behaviour

The infrared (IR) spectra of almandine-grossular and almandine-pyrope garnet solid solutions have been measured using the powder method. Frequency shifts of a band related to internal vibrations associated with the 8-co-ordinate dodecahedral site are nonlinear in almandine-grossular garnets and mimic the form of its molar volume of mixing curve. Almandine-pyrope solid solutions have nearly ideal molar volumes of mixing and the frequency shift of this same 8-co-ordinate site-related band is linear. The IR data support the empirically based crystal chemical model of Equivalent Site (ES) behaviour (Newton and Wood, 1980). The IR spectra give no indication of long-range ordering between Ca and Fe2+ in garnet, but thermodynamic calculations involving Ca-poor garnets might be affected by small volume or short-range ordering anomalies.