Browsing by Author "Dunstan, MT"

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    Complex 5d magnetism in a novel S= 1/2 trimer system, the 12L hexagonal perovskite ba4biir3o12
    (American Chemical Society, 2013-10-21) Miiller, W; Dunstan, MT; Huang, Z; Mohamed, Z; Kennedy, BJ; Avdeev, M; Ling, CD
    The 12L hexagonal perovskite Ba4BiIr3O12 has been synthesized for the first time and characterized using high-resolution neutron and synchrotron X-ray diffraction as well as physical properties measurements. The structure contains Ir3O12 linear face-sharing octahedral trimer units, bridged by corner-sharing BiO6 octahedra. The average electronic configurations of Ir and Bi are shown to be +4(d5) and +4(s1), respectively, the same as for the S = 1/2 dimer system Ba3BiIr2O9, which undergoes a spin-gap opening with a strong magnetoelastic effect at T* = 74 K. Anomalies in magnetic susceptibility, heat capacity, electrical resistivity, and unit cell parameters indeed reveal an analogous effect at T* ≈ 215 K in Ba4BiIr3O12. However, the transition is not accompanied by the opening of a gap in spin excitation spectrum, because antiferromagnetic coupling among S = 1/2 Ir4+ (d5) cations leads to the formation of a S = 1/2 doublet within the trimers, vs S = 0 singlets within dimers. The change in magnetic state of the trimers at T* leads to a structural distortion, the energy of which is overcompensated for by the formation of S = 1/2 doublets. Extending this insight to the dimer system Ba3BiIr2O9 sheds new light on the more pronounced low-temperature anomalies observed for that compound. © 2013, American Chemical Society.
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    Long-range-ordered coexistence of 4-, 5-, and 6-coordinate niobium in the mixed ionic-electronic conductor γ-Ba4Nb2O9
    (American Chemical Society, 2013-07-16) Dunstan, MT; Blanc, F; Avdeev, M; McIntyre, GJ; Grey, CP; Ling, CD
    In a study combining high-resolution single-crystal neutron diffraction and solid-state nuclear magnetic resonance, the mixed ionic-electronic conductor Gamma-Ba4Nb2O9 is shown to have a unique structure type, incorporating niobium in 4-, 5-, and 6-coordinate environments. The 4- and 5-coordinate niobium tetrahedra and trigonal bipyrimids exist in discrete layers, within and among which their orientations vary systematically to form a complex superstructure. Through analysis and comparison of data obtained from hydrated versus dehydrated samples, a mechanism is proposed for the ready hydration of the material by atmospheric water. This mechanism, and the resulting hydrated structure, help explain the high protonic and oxide ionic conductivity of Gamma-Ba4Nb2O9. © 2013, American Chemical Society.
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    Phase behavior and mixed ionic-electronic conductivity of Ba4Sb2O9
    (Elsevier Science BV., 2013-03-21) Dunstan, MT; Pavan, AF; Kharton, VV; Avdeev, M; Kimpton, JA; Kolotygin, VA; Tsipis, EV; Ling, CD
    The 6H-type perovskite phase Ba4Sb2O9, which decomposes in air below 600 K, is found to survive to room temperature in a CO2-free atmosphere. It shows substantial mixed protonic, oxide ionic and electronic conductivity. Compared to Ba4Nb2O9 and Ba4Ta2O9, Ba4Sb2O9 shows higher ionic conductivity due to the relatively easy reducibility of Sb5 +, but lower electronic conductivity due to the predominantly n-type conductivity provided by the Sb5 +/Sb3 + redox couple which leads to reduced hole concentration under oxidizing conditions. Variable temperature synchrotron X-ray diffraction studies carried out in situ under controlled atmospheres reveal a strong monoclinic distortion below 1150 K. The hexagonal to monoclinic transition is slow, does not show second-order behavior, is strongly dependent on atmosphere, and coincides with the loss of ~ 0.4 molecules of H2O per formula unit of Ba4Sb2O9. All of this suggests an important structural role for protons or hydroxide ions in the monoclinic phase. © 2013, Elsevier Ltd.
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    Phase diagram, chemical stability and physical properties of the solid-solution Ba(4)Nb(2-x)Ta(x)O(9)
    (Academic Press INC Elsevier, 2011-10-01) Dunstan, MT; Southon, PD; Kepert, CJ; Hester, JR; Kimpton, JA; Ling, CD
    Through the construction of the Ba4Nb2−xTaxO9 phase diagram, it was discovered that the unique high-temperature γ phase is a thermodynamic intermediate between the low-temperature α phase (Sr4Ru2O9-type) and a 6H-perovskite. Refined site occupancies for the γ phase across the Ba4Nb2−xTaxO9 solid-solution indicate that Nb preferentially occupies the tetrahedral sites over the octahedral sites in the structure. When annealed in a CO2-rich atmosphere, all of the phases studied absorb large amounts of CO2 at high temperatures between ∼ 700 and 1300 K. In situ controlled-atmosphere diffraction studies show that this behaviour is linked to the formation of BaCO3 on the surface of the material, accompanied by a Ba5(Nb,Ta)4O15 impurity phase. In situ diffraction in humid atmospheres also confirms that these materials hydrate below ∼ 1273 K , and that this plays a critical role in the various reconstructive phase transitions as well as giving rise to proton conduction.(C) 2011 Elsevier Inc.
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    Pronounced impact of atmospheric conditions on Ba4Nb2O9 and Ba4Ta2O9
    (Elsvier Science BV, 2012-10-04) Dunstan, MT; Kimpton, JA; Kharton, VV; Ling, CD
    Ba(4)Nb(2)O(9) and Ba(4)Ta(2)O(9) decompose upon heating in a CO(2)-rich atmosphere. Here, we report further in situ synchrotron X-ray diffraction studies under CO(2)-free atmospheres of variable humidity and under vacuum and show that this strongly influences the reconstructive phase transitions normally seen. Under normal atmospheric conditions, alpha-Ba(4)Nb(2)O(9) transforms to gamma-Ba(4)Nb(2)O(9) at 1493 K and alpha-Ba(4)Ta(2)O(9) transforms to 6H-Ba(4)Ta(2)O(9) at 1513 K. Under wet argon, these transitions shift to lower temperatures of 1453 K and 1443 K for Ba(4)Nb(2)O(9) and Ba(4)Ta(2)O(9) respectively. Upon heating both the alpha samples under vacuum, no phase transition is observed at all up to 1723 K. Heating 6H-Ba(4)Ta(2)O(9) under vacuum saw the monoclinic -> hexagonal symmetry-transition temperature increase from 1050 K under air to 1700K. The significance of these observations in terms of possible practical applications of their mixed oxide ionic, protonic and electronic conduction properties are discussed. © 2012, Elsevier Ltd.