Transition-metal substitution in PbAlBO{sub 4}: Synthesis, structural and spectroscopic studies of manganese containing phases
- Kristallographie, FB Geowissenschaften, Universität Bremen, Klagenfurter Straße, D-28359 Bremen (Germany)
- Chemische Kristallographie fester Stoffe, Universität Bremen, Leobener Straße, D-28359 Bremen (Germany)
Highlights: ► Synthesis of mullite-type PbAl{sub 1−x}Mn{sub x}BO{sub 4} by solid state and glycerin methods. ► Fundamental parameter approach describes the X-ray powder diffraction profiles. ► Cell parameters anisotropically change with increasing Mn in the structure. ► Bond valence sums of Pb{sup 2+} linearly correlates eccentricity parameter. ► FTIR spectra confirm the trigonal planar BO{sub 3}. -- Abstract: Mullite-type metal borates PbAlBO{sub 4} with planar BO{sub 3} groups are potential candidates for nonlinear optical properties. We successively substituted aluminum with manganese in the composition PbAl{sub 1−x}Mn{sub x}BO{sub 4}, which would help tuning the crystal chemistry and related physical properties. The end member PbAlBO{sub 4} was synthesized by conventional solid state reaction; the other members of the PbAl{sub 1−x}Mn{sub x}BO{sub 4} series were prepared by glycerin method. The fundamental parameter approach was applied in the Rietveld refinements to describe the X-ray powder diffraction profiles. The cell parameters and interatomic bond distances were studied with respect to the chemical composition x. The MO{sub 6} octahedral distortion linearly increased with the averaged M-O bond distance, which is correlated with the increasing amount of manganese atoms in the structure. The change of the average crystal size and microstrain were explained in terms of Al/Mn ratio in the solid solution. While the empirical bond-valence sums (BVS) of one oxygen atom, bridging the edge-sharing MO{sub 6} octahedron, were found to be under-bonded, the other one was over-bonded. The stereoactivity of the 6s{sup 2} lone electron pair of the Pb{sup 2+} cation was characterized in terms of the absolute value of eccentricity parameter (|Φ{sub i}|). Both bond valence parameter (r{sub 0i}) and BVS of Pb showed a linear correlation with |Φ{sub i}|. Deconvolution of the absorption feature of the infrared powder spectra between 1000 cm{sup −1} and 1400 cm{sup −1} required four fitted bands, which were assigned to B-O stretching vibrations of the trigonal planar BO{sub 3} groups. With increasing Al{sup 3+} dilution in PbAl{sub 1−x}Mn{sub x}BO{sub 4} almost all observed modes shifted toward lower wavenumbers confirming the solid solution. The absorptions caused by the vibrations of the heavy atom Pb were observed in the far-IR region.
- OSTI ID:
- 22215097
- Journal Information:
- Materials Research Bulletin, Vol. 47, Issue 6; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0025-5408
- Country of Publication:
- United States
- Language:
- English
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