Crystal structure refinement of MgSiO₃ high temperature C2/c clinoenstatite

The high-temperature clinoenstatite (HT-CEn) is one of the important MgSiO3 pyroxene polymorph. The single-crystal of C2/c HT-CEn endmember is firstly synthesized by rapid pressure-temperature quenching from 15-16 GPa and 900-1900 ⁰C [1]. No report that it is produced as single crystal or large domain has been made on the MgSiO3 endmember. The HT-CEn-type modifications are observed in Ca-poor Mg-Fe clinoenstatite and pigeonite and are always found to be unquenchable in rapid cooling. The high pressure and high temperature experiments of MgSiO3 composition were carried out with a Kawai-type multi-anvil apparatus. The samples were quenched by rapidly releasing the oil pressure load and/or by blow out of anvil cell gasket. The space group of C2/c is strictly determined by Rigaku RAPID Weissenberg photographs and synchrotron radiation. Single-crystal X-ray diffraction experiments were performed at ambient conditions using a Rigaku AFC-5 four circle diffractometer. A total of 9383 reflections was measured and averaged in Laue symmetry 2/m to give 766 independent reflections used for the structure refinements. Final reliability factors converged smoothly to R = 0.029. The single-crystal diffraction analysis shows that the unusual bonding distances frozen in this metastable structure. The degree of kinking of the silicate tetrahedral chains is 175⁰ for HT-CEn. The chain angle for HP-CEn is substantially smaller (135⁰) and the angle for L-CEn turned to the opposite direction at -160⁰ (=200⁰). The degree of kinking increases by being curved in more than 180⁰ in the transition from HT-CEn to L-CEn. As for the reverse change from the expansion to the stretch, a potential barrier exists in the point of the continuity. It is suggested that the reason which can quench structure under ambient conditions is the present HT-CEn single crystal was formed by the isosymmetric phase transition from HP-CEn. HT-CEn type single-crystals cannot be frozen without pressure.

Structure refinements of kottogite and symplesite solid-solution

Kottogite and symplesite are zinc and ferrous arsenate minerals, respectively. These minerals make the Zn3-x,Fex(AsO4)2·8H2O solid-solution and belongs to the vivianite group of minerals with the chemical formula M3(TO4)2·8H2O. The structure of vivianite and symplesite were determined firstly by Mori and Ito, (1950). The structure of kottigite was refined by Hill, (1979). The strucrure of Zn1.63Fe1.37(AsO4)2·8H2O solid-solution crystallize in space group C2/m with a= 10.342(1), b= 13.484(2), c= 4.7756(5), β=105. 306(4), and Z=2. We performed the structure refinements of (Zn,Fe)3(AsO4)2·8H2O solid-solutions, Ojuela mine, Mapimi Durango, Mexico and Kiura mine, Ohita, Japan by RIGAKU single-crystal structure analysis system RAPID. The R and S values are around 0.03 and 1.08. We determined detail atomic coordinate and hydrogen atom positions. The hydrogen bonds were revealed based on hydrogen positions and bond valence caluculations. The octahedral edge-shareing M2O6(H2O)4 dimers and insular MO2(H2O)4 octahedra are linked by AsO4 terahedra. Two H2O group bonds to (Zn,Fe). Four hydrogen atoms are in the normal hydrogen bonds. Hydrogen atom positions have a tunnel structure and there is a path of proton-conduction and we conjecture that proton conductivity has large anisotropy of one direction. The related minerals, such as paradamite, legrandite and warikahnite have tunnel structure similar to vivianite group.

Distribution of mixed-valence ions in Mn_1+xFe_2-xO₄ ferrites

Mn ferrite has a spinel structure to show the ferrimagnetism, where the magnetic moments show a collinear ferrimagnetic ordering between tetrahedral A and octahedral B sites. Since Mn2+ and Fe3+ have the same electronic configuration, it is not easy to determine the cation distribution of Mn ferrite from usual magnetization measurements. Especially in Mn ferrite, both Mn2+ and Fe3+ have a large spin polarization to give strong magnetic moments through the super exchange interaction between the two sites. Replacing Fe3+ by Mn2+ and Mn4+, the ferrimagnetic property weakens through magnetic balance between the sites. Since Mn and Fe ions may have multiple valences in the oxide structure, the scheme of site preference, based on careful study of various valence states, has been investigated for Mn1+xFe2-xO4. Single crystals for Mn1+xFe2-xO4 (x = 0.05, 0.20, 1.36 and 1.50) were synthesized from stoichiometric proportions of Mn3O4 and Fe3O4 in an evacuated silica capsule at 1353 K for 96 h. Each of spherical or parallel-piped crystals, ranging 0.05 to 0.08 mm, was mounted on the glass fiber. Conventional intensity measurements were made using a Rigaku AFC-5S four-circle diffractometer with a graphite (002) monochromator for Mo Kα radiation. Least-squares refinements were made to obtain atomic parameters, converged with R factors ranging 0.023 to 0.029. The site occupancy of Mn and Fe atoms was then determined on the basis of the resonant scattering effect at the Fe K absorption edge (λ = 1.7535 Å), by using a vertical-type four-circle diffractometer at PF-BL-10A. The results show that 89, 82, 100 and 100 percent of Mn atoms occupy the A site for the four samples, respectively. In the third step of analyses, absorption experiments were performed at PF-BL-6C. XANES and XMCD spectra were used at Mn and Fe K edges for determining the valence states of Mn and Mn ions. Finally, the distribution of mixed-valence ions for Mn1.20Fe1.80O4 was determined by the valence-difference contrast method, where the intensity data were collected for a spherical single crystal of 0.08 mm in a diameter at both threshold and pre-edge regions of Mn K edge, by using an AFC-5u four-circle diffractometer installed in PF-BL-6C. The site occupancy with the valence state will be discussed in the presentation, compared with the other type of transition-metal ferrites.

Substitution effect in high-Tc mercury-based cuprate superconductor

HgBa2Ca2Cu3O8+δ superconductor (Hg-1223) still has the highest critical temperature in various superconductors, which is a layered perovskite with the space group of P4/mmm. A structural unit of cation-layers is stacked in a sequence of -HgO-BaO-CuO-Ca- along the c-axis. The substitution of Hg by Pb enhances the stability of the Hg-1223 phase because the high steam pressure of Hg lowers the chemical stability in synthesis. However, the doping into Hg layers is related to an interstitial oxygen defect. On the other hand, the substitution of Ba by Sr improves the hole doping of CuO2 planes. Thus, the element substitution in Hg and Ba sites becomes a key factor in synthesizing high-quality superconductors. Therefore, the cation distribution in the two sites has been examined by the two-wavelengths anomalous dispersion (TWAD) method of synchrotron X-ray resonant scattering. Single crystals of Hg-1223 were grown at T = 1130 K by the liquid-assisted solid-state recrystallization method from the precursor powder prepared by spray drying or evaporation of the nitrate solutions. Oxygen contents in the precursors were determined by iodometric titrations. Four samples of Hg0.45Pb0.30Ba1.63Sr0.50Ca1.94Cu3O8 (Tc = 128 K), Hg0.42Pb0.41Ba1.19Sr1.06Ca1.97Cu3O8 (125 K), Hg0.50Pb0.50Ba0.59Sr1.24Ca1.83Cu3.34O8 (116 K) and Hg0.34Pb0.54Ba0.61Sr1.17Ca1.88Cu3O8 (115 K) were selected for single-crystal intensity measurements. A conventional measurement to determine the Ba-site occupancy was made to use a Rigaku AFC-5 four-circle diffractometer with Mo Kα radiation. After the absorption correction by the arbitrary-shape grid-integration method, crystal-structure refinements were successfully performed with R factors ranging 6.4 to 6.7 %. The site preference of Hg, Pb and Cu in the Hg site was determined with a vertical-type four-circle diffractometer in PF-BL-10A, where wavelengths of λ = 1.3906 and 1.0191 Å were used at Cu K and Hg LIII absorption edges, respectively. In the TWAD method with least-squares calculations, a variation of the residual factors gives a minimum against the contents of Hg or Cu, suggesting, for example, that Cu does not occupy the Hg site for all samples. In the presentation the site preference and structural change will be discussed in the aspects of superconductivity.

Site-specific RXMS study on the magnetic electron of magnetite

Magnetite Fe3O4 is the best known magnetic mineral for its attractive properties for various magnetic applications. The magnetic moments of Fe atoms show a collinear ferrimagnetic ordering between tetrahedral A and octahedral B sites in an inverse spinel structure with the chemical formula of [Fe3+]A[Fe2+Fe3+]BO4. The distribution of the Fe2+ and Fe3+ over A and B sites is determined by a delicate balance of the crystal field. The geometrical environment of 3d transition metals strongly affects the distribution and the energy state of magnetic electrons which contributes magnetic moments. The resonant x-ray magnetic scattering (RXMS) allows us to make site-selective structural analysis with respect to the magnetic electron. In order to clarify the behavior of the magnetic electrons in magnetite, we carried out the energy-dependent RXMS near Fe K edge. Depends on the observation related to 3d-4p electric transition to empty bands of unpaired electron, we studied the orbital interaction and the density of state of magnetic electrons in A site and B site of magnetite independently. RXMS intensity measurements were performed by using Rigaku AFC-5u four-circle diffractometers at BL-6C of Photon Factory. Circularly-polarized X-rays were produced by a transmitted-type phase retarder of diamond (111). According to the X-ray magnetic circular dichroism (XMCD) spectrum at the Fe K edge, 48 x-ray energies to perform RXMS measurement were selected. The magnetic form factors for various energies were calculated from the difference in diffraction intensities between left- and right-circular polarized measurements. By examining the energy dependence of the resonant magnetic peaks, the density of state of 3d magnetic electron of Fe were obtained for A and B site through the experimental analysis. In the presentation, the interrelationship between the site geometry and the magnetic electrons in terms of energy state will be discussed.

Resonant X-ray magnetic scattering study of Ti-Mn-doped Ba ferrites

BaFe12O19 has M-type hexaferrite structure, giving strong uniaxial anisotropy of the magnetization along c axis. In doped BaTixMnxFe12-2xO19, the substitution of Fe3+ by a pair of Ti4+ and Mn2+ results in a weakening of the magnetic interactions due to the canting of magnetic moments. The crystal structure has a sequence of (Fe6O8) spinel and (BaFe6O11) hcp blocks, associated with five independent Fe sites: tetrahedral 4f1, bipyramidal 2b, and octahedral 2a, 4f2 and 12k sites. Single crystals synthesized by a flux method have cell dimensions of a = 5.8953(2) and c = 23.1887(8) Å and a = 5.9039(2) and c = 23.2047(8) Å for samples of x = 0.5 and 1.0, respectively. Each crystal was mounted with short glass fiber on rare-earth magnet and goniometer head. Conventional intensity measurements were made using a Rigaku AFC7 four-circle diffractometer with a graphite (002) monochromator for Mo Kα radiation. Site-occupancy experiments were performed by using a vertical-type four-circle diffractometer at PF-BL-10A. In this study the magnetic structure has been examined to use resonant X-ray magnetic scattering (RXMS) at the Fe K absorption edge in PF-BL-6C. Circularly polarized X rays produced by a diamond phase retarder were switched between right-handed (helicity=+1) and left-handed polarizations. An AFC-5u four-circle diffractometer was used in the geometry of horizontal scattering plane. Intensity measurements were made to collect as many as possible of Bragg reflections. Based on an asymmetrical ratio of the intensities between right- and left- handed circular polarizations, the intensity difference in the RXMS was estimated for each of reflections. A set of observed asymmetrical ratios was fitted to a model of spin orientation in crystal-structure calculations with the resonant magnetic scattering factors. A residual function in the least-squares fitting is useful to evaluate magnetic moments for individual sites, which is a multiplicity parameter refined in terms of atomic scattering factor. It gives a minimum in plot between site-multiplicity and residual function, assigning the multiplicity related to the canting of magnetic moment in the Fe sites. The magnetic structure obtained in this study is compared with those of M-type BaFe12O19 and BaTiCoFe10O19.

Local structures of Zr in impact-related natural glass probed by XAFS

The local structures of tektites and natural glasses were studied by Zr K-edge XANES and EXAFS in order to provide quantitative data on bonding distances and coordination numbers. The XAFS measurements were performed at the beam line BL-NW10A of the PF-AR in National Laboratory for High Energy Physics (KEK), Tsukuba, Japan. Zr4+ ion in tektite has different kinds of coordination environment. Various natural glasses are formed under different physical conditions. Impact-related glass, fulgurite and volcanic glasses are typical natural glasses. Upon a devastating impact of a giant meteoroid on the Earth, particles of the Earth's surface were melted and catapulted into outer space, where they finally solidified and fell back to the Earth. Tektites should be formed by this series of processes [1]. Tektite has special local structure of Ca[2]. Glass structure is affected by the pressure and temperature conditions during the glass formation and quenching process. This study indicated that different formation process of natural glasses gives different local structure of zirconium ions. The Zr K-edge XANES spectra of tektite have the double post-edge peaks with different heights. The volcanic glasses and other impact-related glasses such as impactite possessed more simple XANES patterns. The average coordination number of Zr4+ in darwin glass, LDG, volcanic glass and tektite are between 6 and 7. The eight-coordinated Zr4+ shows different XAFS pattern in suevite and köfelsite. All tektites are classified in same type. According to EXAFS measurements, Zr-O distances in tektites are 2.198 - 2.215Å and XANES spectra of tektites have similar shape. It indicates that tektites have similar Zr local structure with 7-fold coordination Zr ions. Impact-related glasses are classified to different types. Volcanic glasses are classified to same types. Impact glasses are formed under different geological processes at impact event and are experienced different physical environments.

Magnetic electron density in Fe3O4 examined by RXMS at Fe K edge

"It is known that a difference-Fourier synthesis of the Fourier series provides a mean for the location of bonding electrons, by subtracting out the electron density of all atoms in the crystal structure. Here the Fourier technique in X-ray diffraction was applied to observe the magnetic electron density of magnetite Fe3O4. An asymmetrical ratio in the resonant X-ray magnetic scattering (RXMS) provides information on the magnetic moments, which can be estimated from an intensity difference between the right-handed and left-handed polarized X rays. The ratio is proportional to the real part of the product of the spin-contributed structure factor F(hkl) and the complex conjugation of charge-scattered F(hkl). Expanding the equations in difference–Fourier formalization, the spin density can be represented with the observed f""m of RXMS. Synchrotron RXMS experiments were performed at the PF-BL-6C beamline using an AFC-5u four-circle diffractometer. Through a diamond phase retarder the incident X rays were circularly polarized at the Fe K absorption edge, where a wavelength of λ = 1.7439 Å (E = 7.1094 keV) was selected within the pre-edge. A spherical crystal of 0.13 mm in diameter was mounted along the a3 axis with the glass fiber on rare-earth magnet and goniometer head. The intensity data of RXMS were collected for Bragg reflections up to 2θ = 131⁰. After crystal-structure refinements with scaling of the RXMS data, difference-Fourier syntheses were made in triclinic symmetry with a total of 165 reflections by using the software FRAXY. The syntheses are superior in examining the magnetic effect in the polarization difference and eliminating other effects such as charge scattering, experimental errors and the termination effect. The difference of magnetic electron density between left-handed and right-handed circular polarizations at E was estimated in the Fourier series of partially observed F(hkl). The magnetic electron density on Fourier maps will be discussed in the presentation."