| 1. |
- Jacobsen, Henrik, et al.
(författare)
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Spin dynamics of the director state in frustrated hyperkagome systems
- 2021
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Ingår i: Physical Review B. - : American Physical Society. - 2469-9969 .- 2469-9950. ; 104:5
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Tidskriftsartikel (refereegranskat)abstract
- We present an experimental study of the magnetic structure and dynamics of two frustrated hyperkagome compounds, Gd3Ga5O12 and Gd3Al5O12. It has previously been shown that Gd3Ga5O12 exhibits long-range correlations of multipolar directors that are formed from antiferromagnetic spins on loops of ten ions. Using neutron diffraction and reverse Monte Carlo simulations we prove the existence of similar magnetic correlations in Gd3Al5O12, showing the ubiquity of these complex structures in frustrated hyperkagome materials. Using inelastic neutron scattering we shed further light on the director state and the associated low-lying magnetic excitations. In addition, we have measured quasielastic dynamics that show evidence of spin diffusion. Finally, we present AC susceptibility measurements on both Gd3Ga5O12 and Gd3Al5O12, revealing a large difference in the low-frequency dynamics between the two otherwise similar compounds.
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| 2. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Structural study and proton conductivity of BaZr0.90Ga0.10O2.95
- 2006
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Ingår i: Advances of Solid Oxide Fuel Cells II, Ceramic Engineering and Science Proceedings. - Hoboken, NJ, USA : John Wiley & Sons, Inc.. ; 27:4, s. 105-117
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Tidskriftsartikel (refereegranskat)abstract
- Traditional solid state sintering has been used to prepare the perovskite BaZr0.9Ga0.1O2.95. Analysis of X-ray powder diffraction data shows that a decrease of the unit cell parameter a was observed compared to the undoped BaZrO3, which confirms successful substitution of Ga3+ for Zr4+ at the B site. Rietveld analysis of room temperature neutron powder diffraction data confirmed cubic symmetry (space group Pm-3m) for both as- prepared and deuterated BaZr0.90Ga0.10O2.95 samples. The strong O-H stretch band (2500-3500 cm−1) in the infrared absorbance spectrum clearly manifests the presence of protons in the pre-hydrated material. The bulk and total conductivities of prehydrated BaZr0.9Ga0.1O2.95 are 1.17 × 10−5 and 3.55 × 10−6 Scm−1, respectively at 400°C, which are more than one order of magnitude higher than for dried a sample at the same temperature. In contrast, the total conductivity of pre-hydrated and dried samples is similar at higher temperature, e. g. T > 800 °C. The higher activation energy (e. g. 0.7 eV) for pre-hydrated sample compared to typical value (0.4-0.5 eV) of proton conduction may suggest that the protons are trapped in the material.
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| 3. |
- Andersson, A. K. E., et al.
(författare)
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Chemical Expansion Due to Hydration of Proton-Conducting Perovskite Oxide Ceramics
- 2014
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Ingår i: Journal of the American Ceramic Society. - : Wiley. - 0002-7820 .- 1551-2916. ; 97:8, s. 2654-2661
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Tidskriftsartikel (refereegranskat)abstract
- The crystal structures of proton-conducting BaZr1-xYxO3-x/2 (BZY05-BZY20) and BaCe0.8Y0.2O2.9 (BCY20) during hydration/dehydration has been studied by in situ high-temperature X-ray diffraction and thermal analysis. A contraction/expansion of the crystal lattice associated with dehydration/hydration was observed for all materials at elevated temperatures and the polymorphic phase transition temperatures of BaCe0.8Y0.2O2.9 were depressed by lowering the vapor pressure of water. A thermodynamic formalism is introduced to describe the chemical expansion associated with the hydration of oxygen vacancies in acceptor-doped oxides. A conventional point defect model was applied to describe the lattice strain associated with the hydration. The chemical expansion is discussed with respect to the available volumetric data on the hydration of proton-conducting oxide materials and its likely impact on ceramic fuel cells/hydrogen separation membranes utilizing a proton-conducting electrolyte.
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| 4. |
- Bjorheim, T. S., et al.
(författare)
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Hydration thermodynamics of the proton conducting oxygen-deficient perovskite series BaTi1- xMxO3- x /2 with M = in or Sc
- 2015
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 54:6, s. 2858-2865
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Tidskriftsartikel (refereegranskat)abstract
- This article establishes the effect of structure and composition on water uptake and the hydration and proton transport properties of the oxygen-deficient perovskite series BaTi1-x(In,Sc)xO3-x/2, with 0.2 ≤ x ≤ 0.7. The equilibrium water uptake is determined by thermogravimetry, while combining thermogravimetry with differential scanning calorimetry allows for direct determination of the materials hydration thermodynamics. Proton and oxide ion transport properties are characterized by means of ac impedance measurements up to 1000 °C. In general, the hydration thermodynamics of the scandates are more favorable than that of the indates and are also affected by changes in crystal structure throughout the series. The more favorable hydration thermodynamics of cubic scandates increase their proton conductivity at higher temperatures compared to their indate counterparts. In contrast to the BaTi1-xInxO3-x/2 series, the BaTi1-xScxO3-x/2 (0.5 ≤ x ≤ 0.7) materials retain their cubic structures upon full saturation by protons and show no signs of chemical instability upon exposure to 1 atm H2O(g) down to 100 °C. The BaTi1-xScxO3-x/2 materials with 0.5 ≤ x ≤ 0.7 may therefore find application in, for instance, steam electrolysis or similar processes involving high water vapor pressures.
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| 5. |
- Eriksson Andersson, A.K., et al.
(författare)
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Thermal evolution of the crystal structure of proton conducting BaCe 0.8 Y 0.2 O 3-δ from high-resolution neutron diffraction in dry and humid atmosphere
- 2015
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 44:23, s. 10834-10846
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Tidskriftsartikel (refereegranskat)abstract
- The crystal structure of the proton conducting perovskite BaCe0.8Y0.2O3-δ (BCY20) has been studied via high-resolution in situ neutron diffraction performed in controlled dry and humid (heavy water) oxygen flow. Two phase transitions, cubic Pm3m→R3c (775 °C)→Imma (250 °C) were observed on cooling from 1000 °C in dry O2. A significant shift of the phase stability fields was observed on cooling in wet oxygen (pD2O ≈ 0.2 atm) with the R3c structure stabilised at 900 °C, and the R3c→Imma transition occurring at 675 °C. On cooling below 400 °C a monoclinic, I2/m, phase started to appear. The structural dependence on hydration level is primarily due to the de-stabilisation of the correlated, octahedra tilts as a consequence of structural relaxation around the oxygen vacancies present in the non-hydrated phase. The tendency of hydrated BaCe0.8Y0.2O3-δ to show octahedral tilting is also found to be enhanced, indicating that the deuteronic (protonic) defects influence the crystal structure, possibly via hydrogen bonding. Stabilisation of the monoclinic I2/m phase is attributed to the structural effect of deuterons that is inferred to increase on cooling as deuterons localise to a greater extent. Changing from wet oxidising (O2 + D2O(g)) to wet reducing (5% H2 in Ar + D2O(g)) atmosphere did not influence the structure or the phase stability, indicating that Ce4+ was not reduced under the present conditions. Based on the observed cell volume expansion protonic defects are present in the material at 900 °C at a D2O partial pressure of ∼0.2 atm. The origin of the chemical expansion is explained by the effective size of the oxygen vacancy being significantly smaller than the [OD] defect. Rietveld analysis has been used to locate possible sites for the deuterons in the high temperature, R3c and Imma, phases that are most relevant for proton transport.
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| 6. |
- Kalland, L. E., et al.
(författare)
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C-type related order in the defective fluorites La2Ce2O7 and Nd2Ce2O7 studied by neutron scattering and ab initio MD simulations
- 2016
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 18:34, s. 24070-24080
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Tidskriftsartikel (refereegranskat)abstract
- This work presents a structural investigation of La2-xNdxCe2O7 (x = 0.0, 0.5, 1.0, 1.5, 2.0) using X-ray powder diffraction and total scattering neutron powder diffraction, analysed using Rietveld and the reverse Monte Carlo method (RMC). Ab initio molecular dynamics (MD) modelling is also performed for further investigations of the local order. The main intensities in the neutron diffraction data for the La2-xNdxCe2O7 series correspond to the fluorite structure. However, additional C-type superlattice peaks are visible for x > 0 and increase in intensity with increasing x. The Nd-containing compositions (x > 0) are best fitted with Rietveld analysis by using a combination of oxygen deficient fluorite and oxygen excess C-type structures. No indications of cation order are found in the RMC or Rietveld analysis, and the absence of cation order is supported by the MD modelling. We argue that the superlattice peaks originate from oxygen vacancy ordering and associated shift in the cation position away from the ideal fluorite site similar to that in the C-type structure, which is seen from the Rietveld refinements and the observed ordering in the MD modelling. The vacancies favour alignments in the , and especially the direction. Moreover, we find that such ordering might also be found to a small extent in La2Ce2O7, explaining the discernible modulated background between the fluorite peaks. The observed overlap of the main Bragg peaks between the fluorite and C-type phase supports the co-existence of vacancy ordered and more disordered domains. This is further supported by the observed similarity of the radial distribution functions as modelled with MD. The increase in long range oxygen vacancy order with increasing Nd-content in La2-xNdxCe2O7 corresponds well with the lower oxide ion conductivity in Nd2Ce2O7 compared to La2Ce2O7 reported earlier.
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| 7. |
- KINYANJUI, FRANCIS GACHAO, 1981, et al.
(författare)
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Crystal structure and proton conductivity of BaSn0.6Sc0.4O3-delta: insights from neutron powder diffraction and solid-state NMR spectroscopy
- 2016
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488 .- 2050-7496. ; 4:14, s. 5088-5101
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Tidskriftsartikel (refereegranskat)abstract
- The solid-state synthesis and structural characterisation of perovskite BaSn(1-x)ScxO(3-delta)(x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pm (3) over barm) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. Sn-119 and Sc-45 solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D2O. It also indicates that the Sn4+ and Sc3+ local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x = 0.3). O-17 NMR spectra on O-17 enriched BaSn1-xScxO3-delta materials show the existence of Sn-O-Sn, Sn-O-Sc and Sc-O-Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn0.6Sc0.4O3-delta refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O-D bond distance of 0.96(1) angstrom and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 degrees C with total conductivity values in the range 1.8 x 10(-4) to 1.1 x 10(-3) S cm(-1) between 300 and 600 degrees C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 degrees C temperature region, and a suppression of the conductivity at higher temperature.
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| 8. |
- Norberg, Stefan, 1972, et al.
(författare)
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The proton conducting electrolyte BaTi0.5In0.5O2.75: determination of the deuteron site and its local environment
- 2013
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Ingår i: Journal of Physics Condensed Matter. - : IOP Publishing. - 0953-8984 .- 1361-648X. ; 25:45
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Tidskriftsartikel (refereegranskat)abstract
- Deuterated BaTi0.5In0.5O2.75 has been studied with neutron total (Bragg plus diffuse) scattering data, using both the Rietveld refinement method and the reverse Monte Carlo (RMC) modelling technique, to investigate the preferred proton site and its local structural environment. The Rietveld analysis shows an excellent fit between experimental data and a long-range cubic description of the BaTi0.5In0.5O2.53(OD)(0.44) perovskite structure containing a statistical distribution of Ti and In ions at the centre of regular (Ti/In)O-6 octahedra. However, an RMC analysis of the data reveals substantial local structural features that reflect limitations of the Rietveld method for studies of this type. The Ti-O and In-O pair distribution functions given by the RMC analysis are markedly different from each other, with average Ti-O and In-O bond distances of 2.035 angstrom and 2.159 angstrom, respectively. The InO6 octahedra are regular in shape whereas the TiO6 octahedra are distorted. The average O-D bond distance is roughly 0.96 angstrom, and the preferred deuteron sites have a second nearest oxygen distance of 2.13 angstrom, which confirms localized tilting of the deuteron and indicates a substantial degree of hydrogen bonding. The impact of octahedral distortion and hydrogen bonding on the proton conduction mechanism is discussed.
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| 9. |
- Rahman, Habibur Seikh Mohammad, 1976, et al.
(författare)
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Proton conductivity of hexagonal and cubic BaTi1-xScxO3-δ (0.1 ≤ x ≤ 0.8)
- 2014
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Ingår i: Dalton Transactions. - 1477-9226 .- 1477-9234. ; 43:40, s. 15055-15064
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Tidskriftsartikel (refereegranskat)abstract
- BaTi1−xScxO3−δ (x = 0.1–0.8) was prepared via solid state reaction. High resolution X-ray powder diffraction was used to characterise the synthesised materials. It was found that low substitution (x = 0.1 and 0.2) of Ti4+ for Sc3+ gives a hexagonal perovskite structure, whereas high substitution (x = 0.5–0.7) results in a cubic perovskite structure. Thermogravimetric analysis revealed significant levels of protons in both as-prepared and hydrated samples. Electrical conductivity was measured by AC impedance methods under oxygen, argon and under dry and humid, both H2O and D2O, conditions for BaTi1−xScxO3−δ (x = 0.2, 0.6 and 0.7). In the temperature range of 150–600 °C, under humid conditions, the conductivity is significantly higher than that under the dry conditions. The increase in conductivity is especially prominent for the cubic phases, indicating that protons are the dominant charge carriers. The proton conductivity of hexagonal BaTi0.8Sc0.2O3−δ is approx. two orders of magnitude lower than that of the more heavily substituted cubic phases. Conductivity is also found to be higher in dry O2 than in Ar in the whole temperature range of 150–1000 °C, characteristic of a significant contribution from p-type charge carriers under oxidising atmospheres. Greater Sc3+ substitution leads to a higher proton concentration and the highest proton conductivity (σ [similar] 2 × 10−3 S cm−1 at 600 °C) is found for the BaTi0.3Sc0.7O3−δ composition.
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| 10. |
- Torino, Nico, 1982, et al.
(författare)
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The influence of cation ordering, oxygen vacancy distribution and proton siting on observed properties in ceramic electrolytes: the case of scandium substituted barium titanate
- 2017
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 46:26, s. 8387-8398
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Tidskriftsartikel (refereegranskat)abstract
- The origin of the 2-order of magnitude difference in the proton conductivity of the hydrated forms of hexagonal and cubic oxygen deficient BaScxTi1-xO3-delta (x = 0.2 and x = 0.7) was probed using a combination of neutron diffraction and density functional theory techniques to support published X-ray diffraction, conductivity, thermogravimetric and differential scanning calorimetry studies. Cation ordering is found in the 6H structure type (space group P6(3)/mmc) adopted by BaSc0.2Ti0.8O3-delta with scandium preferentially substituting in the vertex sharing octahedra (2a crystallographic site) and avoiding the facesharing octahedra (4f site). This is coupled with oxygen vacancy ordering in the central plane of the facesharing octahedra (O1 site). In BaSc0.7Ti0.3O3-delta a simple cubic perovskite (space group Pm3m) best represents the average structure from Rietveld analysis with no evidence of either cation ordering or oxygen vacancy ordering. Significant diffuse scattering is observed, indicative of local order. Hydration in both cases leads to complete filling of the available oxygen vacancies and permits definition of the proton sites. We suggest that the more localised nature of the proton sites in the 6H structure is responsible for the significantly lower proton conduction observed in the literature. Within the 6H structure type final model, proton diffusion requires a 3-step process via higher energy proton sites that are unoccupied at room temperature and is also likely to be anisotropic whereas the highly disordered cubic perovskite proton position allows 3-dimensional diffusion by well-described modes. Finally, we propose how this knowledge can be used to further materials design for ceramic electrolytes for proton conducting fuel cells.
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