Crystal structure and thermal behavior of Bi ₆ Te ₂ O ₁₅:Investigation of synthetic and natural pingguite

The previously unknown crystal structure of pingguite was determined and refined from laboratory X-ray powder diffraction data using a synthetic sample. Additional single crystal diffraction of natural pingguite confirms that the crystal structure of the synthetic sample is identical to the natural mineral. This new crystal structure calls for a revised chemistry of the rare mineral pingguite to Bi6Te2O15 instead of the previously reported formula Bi6Te2O13. Pingguite contains TeVI only and not TeIV as previously reported. Pingguite undergoes an irreversible phase transition around 840 ∘C which is characterized by a loss of oxygen and a reduction from TeVI to TeIV resulting in a δ-Bi2O3 like type structure. In addition, we report the Raman spectroscopic data on the natural pingguite

Strontium doping in mullite-type bismuth aluminate: A vacancy investigation using neutrons, photons and electrons

We report on strontium doped dibismuth-nonaoxoaluminate(III) produced at 1023 K. Partial substitution of bismuth by strontium in the structure yields oxygen vacancies for charge balance. Introducing oxygen vacancies rearranged the associated Al2O7 double-tetrahedra forming “Al3O10” tri-clusters which were identified by multi-quantum 27Al MAS NMR. Both STEM-EDX and XPS showed homogeneous distribution of strontium in the bulk and on the surface, respectively. Moreover, XPS confirms the valence state of bismuth after doping. The orientations of bismuth 6s2 lone electron pairs were calculated using DFT methods. The amount of strontium in the crystal structure was further confirmed from the decomposition product SrAl12O19 formed during the temperature-dependent X-ray powder diffraction. The structural proof was carried out by refining the structure of (Bi0.94Sr0.06)2Al4O8.94 from powder neutron and X-ray diffraction data. Rietveld refinements clearly showed the under occupation of one oxygen site and the shift of two aluminum atoms from the double-tetrahedra to two tri-cluster sites

Proper ferroelectric transition in the multiferroic YMnO3

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Crystal chemical characterization of mullite-type aluminum borate compounds

Al-rich aluminum borates were prepared by different synthesis routes using various Al/B ratios, characterized by diffraction methods, spectroscopy and prompt gamma activation analysis. The 11B NMR data show a small amount of BO4 species in all samples. The chemical analysis indicates a trend in the Al/B ratio instead of a fixed composition. Both methods indicate a solid solution Al5−xB1+xO9 where Al is substituted by B in the range of 1–3%. The structure of B-rich Al4B2O9 (C2/m, a=1488 pm, b=553 pm, c=1502 pm, ß=90.6°), was re-investigated by electron diffraction methods, showing that structural details vary within a crystallite. In most of the domains the atoms are orderly distributed, showing no signal for the postulated channel oxygen atom O5. The absence of O5 is supported by density functional theory calculations. Other domains show a probable disordered configuration of O5 and O10, indicated by diffuse scattering along the b direction.17318

Magnetic structures of the low temperature phase of Mn3(VO4)2– towards understanding magnetic ordering between adjacent Kagomé layers

In this article we report on a detailed analysis of the magnetic structures of the magnetic phases of the low temperature (lt-) phase of Mn3(VO4)2 ([double bond, length as m-dash]Mn3V2O8) with a Kagomé staircase structure determined by means of powder neutron diffraction. Two magnetic transitions were found at ∼25 K (HT1 phase, Cmc′a′) and ∼17 K (LT1 phase, Pmc′a′), in excellent agreement with previous reports. The LT1 phase is characterized by commensurate magnetic ordering of the magnetic moments on two magnetic sites of the Mn1a/b (2a + 2d) and Mn2 (8i) ions of the nuclear structure (where for the latter site two different overall orientations of magnetic moments within the ab-plane (Mn2a and Mn2b) can be distinguished. This results in mainly antiferromagnetic interactions between edge-sharing Mn-octahedra within the Kagomé planes. The HT1 phase is characterised by strong spin frustration resulting from the loss of ordering of the magnetic moments of Mn2a/b ions along the b-axis. Both magnetic structures are in agreement with the previously reported ferrimagnetic properties of lt-Mn3(VO4)2 and shed light on the magnetic phase diagram of the compound reported previously. The magnetic structures are discussed with respect to superexchange interaction pathways within the Kagomé layers, which appear to be predominantly antiferromagnetic. The magnetic structures of Mn3(VO4)2 are different compared to those reported for Ni3(VO4)2 and Co3(VO4)2 and represent an unique commensurate way out of spin frustration for compounds with strong antiferromagnetic superexchange interactions within the Kagomé layers. Additionally, we derive a superexchange model, which will be called redox-mediated M–M′(d0)–M superexchange and which can help to understand the exclusively ferromagnetic ordering of adjacent Kagomé layers found only for lt-Mn3(VO4)2

Oxygen vacancy ordering in SrFe0.25Co0.75O2.63 perovskite material

International audienceSrFe0.25Co0.75O2.63 was synthesized by a solid-state reaction. Its structural study at room temperature using conventional X-ray as well as neutron powder diffraction, electron diffraction and high-resolution transmission electron microscopy is presented. An oxygen-vacancy ordering related to the “314” model known for the Sr3Y1Co4O10.5 oxide is proposed despite neither an A-site ordering nor an A-site mismatch. By means of Mössbauer spectroscopy, Mohr salt titration and the difference in the neutron cross sections of Fe and Co, a cation distribution within the crystallographic sites as the following Sr4(Fe0.143+Co0.363+)48h(Fe0.114+Co0.144+Co0.253+)48fO10.52 is suggested, highlighting a natural layered structure with Fe and Co in higher oxidation states in the oxygen replete layers than in the oxygen deficient ones