Eligio Orozco

The crystal structure of InYGe2O7 germanate

Abstract A new indium yttrium germanate presenting the thortveitite structure with symmetry described by the space group C2/m (No. 12) has been prepared by high temperature solid state reaction as polycrystalline powder material. This crystallizes in the monoclinic system, with cell parameters a = 6.8286(1) Å, b = 8.8836(2) Å, c = 4.9045(1) Å, β= 101.8340(7)º, V = 291.195(9) Å3 and Z = 2. The structure was characterized by X-ray powder diffraction and Rietveld refinement of the diffraction pattern. The In3+ and Y+3 cations occupy the same octahedral site forming a hexagonal arrangement on the ab planes. In their turn, the hexagonal arrangements of InO6/YO6 octahedral layers are held together by sheets of isolated diorthogroups constituted by a double tetrahedra sharing a common vertex. In this compound, the Ge2O7 diorthogroup shows the C2h symmetry implying a Ge-O-Ge angle of 180º, being an important feature of the thortveitite structure, which has been controversial in some reported papers. A remarkable photo-luminescence effect (in comparison with glass) was observed when the sample was irradiated with α-particles beam during the RBS experiments employed to analyze the chemical stoichiometry.

The crystal structure of FeInGe2O7

Abstract A new iron indium germanate has been prepared as polycrystalline powder material which crystallizes in the monoclinic system (S.G. C2/m, No. 12). The structure was characterized by X-ray powder diffraction and Rietveld refinement of the resulting diffraction pattern. The cell parameters are a = 6.5124(4) Å, b = 8.5914(5) Å, c = 4.8936(3) Å, β = 102.683(2)°, V = 267.12(3) Å3 and Z = 2. The structure contains R+3 cations (R=Fe, In) almost equally distributed in distorted RO6 octahedral sites. These octahedra are joined by edge sharing forming a hexagonal arrangement on the ab planes. The RO6 octahedra layers are held together by sheets of isolated Ge2O7 diorthogroups constituted by a double tetrahedra sharing a common vertex. This compound has the thortveitite structure and keeps a strong relationship with the FeYGe2O7 germanate, which presents two R+3 sites with six-coordinated (R=Fe) and seven-coordinated (R=Y) oxygens, corresponding to the different symmetry given by the monoclinic space group P21/m (No. 11)

Grain growth and phase transformations induced by shock waves on alpha-GeO2 powder

An impact experiment on a mixture of water and microcrystalline alpha-GeO2 powder was performed with a single-stage gas gun. The recovered sample contained micrometer-scale crystals of different sizes and morphologies that correspond to 88% of alpha-GeO2, 6.0% of monoclinic phase (P21/c, space group No. 14), 4.9% of orthorhombic phase (Pnnm, space group No. 58) and 1.1% of rutile-type phase.

A synchrotron study of Na2.27Ho7.73(SiO4)6O0.72

A well crystallized powder sample of sodium holmium orthosilicate oxyapatite, Na2.27Ho7.73(SiO4)6O0.72, was obtained after mechanical milling and thermal treatment at 1123 K. Crystal structure analysis was performed from the results of Rietveld refinement of the synchrotron diffraction data. As in other rare-earth orthosilicate apatites, sodium cations appear located sharing with holmium the 4f Wyckoff position at the center of a tricapped trigonal prism. In its turn, holmium almost fully occupies the 6h position at the center of a seven-coordinated pentagonal bipyramid. A small quantity of Na atoms was found at this site. No vacancies are present in the two independent crystallographic sites available for Ho and Na atoms.

Raman analysis of an impacted α-GeO2–H2O mixture

Through a Raman analysis, we detected polymorphism at high pressure on mixtures of α-GeO2 microcrystalline powder and water under impact experiments with a single-stage gas gun. The Raman measurements taken from recovered samples show two vibrational modes associated with water-related species. After the impact, the size of the α-GeO2 crystallites was approximately 10 times higher showing molten zones and a lot of porous faces. Raman examination showed some unknown peaks possibly associated with other GeO2 polymorphs detected by X-ray diffraction experiments and perhaps stabilized in the porous of the α-GeO2 crystallites.

Structural characterization of SmMn2GeO7 single microcrystals by electron microscopy

Single microcrystals of the new compound samarium dimanganese germanium oxide, SmMn2GeO7, were grown using the flux method in a double spherical mirror furnace (DSMF). The micrometric crystals were observed and chemically analysed with scanning electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDX). The structural characterization and chemical analysis of these crystals were also carried out using transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), together with electron-energy-loss spectroscopy (EELS). We found that the new quaternary compound crystallizes in the orthorhombic system with the point group mmm (D2h), space group Immm (No. 71) and cell parameters a=8.30 (10), b=8.18 (10), c=8.22 (10) A and V=558.76 A3.

Phase transitions induced by shock compression on a gypsum mineral: X-ray and micro-Raman analysis

As a part of systematic researches of phase transitions induced by shock compression in phosphates, silicates, germanates and sulfates, in this article we report preliminary results obtained from shock recovery experiments on powders of a gypsum mineral. The shock experiment was performed in a light gas gun until a pressure close to 14 GPa reached. The experimental techniques employed to analyze the shock effects on recovered samples were: Scanning Electron Microscopy (SEM), X-ray Powder Diffraction (XRD) and Micro-Raman Spectroscopy (MRS). The SEM observations show a high plasticity in the impacted sample composed mainly by gypsum and bassanite quantified by Rietveld analysis of the XRD. The results indicate the partial dehydration of gypsum as a result of impact. The MRS analysis suggests the presence of micro-mixtures of gypsum, bassanite and anhydrite heterogeneously distributed throughout the recovered sample.

Y0.76Ho0.24FeGe2O7: a new member of thortveitite-like layered compounds

Y0.76Ho0.24FeGe2O7 (yttrium holmium iron digermanate) was synthesized by solid-state reaction at 1573 K. This thortveitite-like compound presents a crystallographic group–subgroup isotranslational (klassengleiche) relation with some other pyrogermanates, such as FeInGe2O7, In1.08Gd0.92Ge2O7 and InYGe2O7, which are configurationally isotypic with the Sc2Si2O7 thortveitite structure first reported by Zachariasen [(1930 ▶). Z. Kristallogr. 73, 1–6]. Holmium cations share with yttrium the 4f Wyckoff position at the center of a seven-coordinated pentagonal bipyramid, while Fe atoms also occupy one site with Wyckoff position 4f at the center of the octahedron. All these sites have the point symmetry C 1. Two types of Ge2O7 diorthogroups with point symmetry C 1h are present in the structure, each one of them defining a layer type which alternates with the other. These diorthogroups have their tetrahedral groups in an eclipsed conformation.

In1.08Gd0.92Ge2O7: a new member of the thortveitite family.

Indium gadolinium digermanium heptaoxide, In(1.08)Gd(0.92)Ge(2)O(7), with a thortveitite-type structure, has been prepared as a polycrystalline powder material by a high-temperature solid-state reaction. As in the mineral thortveitite, the crystal structure belongs to the monoclinic system, with space group C2/m (No. 12). The precise structural parameters were obtained by applying the Rietveld method of refinement to the X-ray powder diffraction data. This layered structure presents, on one side, a honeycomb-like arrangement of the unique octahedral site, which is occupied randomly by In and Gd atoms, and, on the other side, sheets of isolated Ge(2)O(7) diortho-groups made up of double tetrahedra sharing a common vertex and displaying C(2h) point symmetry. This compound showed a remarkable photoluminescence effect when it was irradiated with the X-ray beam during the X-ray diffraction measurements, and with the alpha beam during the Rutherford back-scattering spectrometry experiments employed to analyze the chemical stoichiometry.

Hydration reactions in tricalcium silicate by XRD and combined techniques

The tricalcium silicate hydration products were studied by quantitative analysis by the Rietveld method of crystalline phases at time intervals of 30 min, 4 hours, as well as 1, 7, 14, 21 and 28 days. The evolution of the different phases present was further studied by differential scanning calorimetry, thermogravimetric analysis, pH, chemical analysis and compressive strength. Combining the results of the crystalline phase composition and thermogravimetric analysis, a procedure was established to estimate the amount of amorphous calcium silicate hydrate (CSH) as a function of time, as well as the proportion of portlandite and other phases. The results showed a complete hydration reaction at 28 days, during which the tricalcium silicate disappears completely. The formation of portlandite occurs at 24 hours and subsequently shows a tendency to decrease, while CSH increases its proportion during the time interval studied. At 30 min and at 4 hours, no changes were observed in the phase composition of the hydrated paste. From chemical analysis, the CSH can have a structural arrangement of the jaffeite type [1] or other structural types than can be discussed in the presentation. The cohesion of CSH particles is analyzed on the light of the model suggested by Jönsson [2]. The figure below shows a Rietveld refinement for the sample paste at 21 days of hydration. [1]. Richardson I.G. (2008). Cement and concrete research 38, 137-158. [2]. Jönsson B. (2004). Langmuir 20, 6702–9.