Stability and Evolution of the Crystal Structure of TbBaCo2O6-δ During Thermal Oxygen Release/Uptake.

A-site ordered double perovskites with the general formula LnBaCo2O6-δ (where Ln is a lanthanide element) present electrical and electrocatalytic properties that make them attractive as possible ceramic electrode materials for solid oxide cells or alkaline electrolyzers. The properties are highly influenced by the anion vacancy concentration, which is strongly related to the Co-oxidation state, and their location in the structure. Awareness of the stable phases is essential to synthesize, evaluate, and optimize the properties of LnBaCo2O6-δ oxides at operating conditions in different applications. TbBaCo2O6-δ are representative oxides of these layered perovskite systems. The present article reports a study of TbBaCo2O6-δ by electron diffraction, high-resolution electron microscopy, and powder neutron diffraction experiments at different temperatures. The synthesis of TbBaCo2O6-δ in air and slow cooling to room temperature (RT) at 5 °C h-1 leads to samples formed by distinct phases with different oxygen contents and crystal structures. The 122 and 112 phases (with ap × 2ap × 2ap and ap × ap × 2ap unit cells, respectively, with ap being the lattice parameter of the simple cubic perovskite structure) are predominant in quasi-equilibrium prepared samples (cooled at RT at 1 °C h-1) or prepared in Ar flow and quenched to RT. The evolution of the crystal structure of TbBaCo2O6-δ during thermal oxygen release/uptaking consists of modulation from the 122 phase to the 112 phase (or vice versa during uptaking) by creation/occupation of anion vacancies within the TbO1-δ planes. Anion vacancies are not detected in the oxygen crystallographic position different from those located within the TbO1-δ planes even at the highest temperatures, supporting the 2D character of the high anion conduction of the LnBaCo2O6-δ oxides.

Antibacterial Ability of Sodium Hypochlorite Activated with PUI vs. XPF File against Bacteria Growth on Enterococcus faecalis Mature Biofilm.

The objectives of the present study were to assess the antibacterial effectiveness of two sodium hypochlorite (NaOCl) concentrations (2.5% and 5.25%) activated by means of two techniques, passive ultrasonic irrigation (PUI) and XP-endo® Finisher (FKG Dentaire SA, La Chaux-de-Fonds, Switzerland) (XPF) against bacteria growth in intracanal mature biofilm. Our aim was to determine if the effect of heating up NaOCl at body temperature (BT) contributed to an improvement of the efficacy of XPF. Sixty-two single-canal human roots previously instrumented were infected with E. faecalis inoculum at 0.5 McFarland and incubated at 37 °C for two weeks. Twelve specimens were randomly selected as positive control, and the remaining fifty were divided into five experimental groups (n = 10). The first two were irrigated with 2.5 vs. 5.25% NaOCl at room temperature (RT), activated with PUI, and the other three were irrigated with XPF. Of these three, two were irrigated using 2.5 vs. 5.25% NaOCl at RT and one was irrigated with 5.25% NaOCl at BT. Our results showed that NaOCl was effective in biofilm removal for all experimental groups (p > 0.05), especially in the groups irrigated with 5.25% NaOCl at room temperature (RT) activated with PUI and the group treated with 5.25% NaOCl at BT with XPF. These groups were the most successful ones (p < 0.001). NaOCl, activated with XPF, was as effective as PUI in biofilm removal from the apical third of the canal when it was used at higher concentration and heated up. This study indicates that XPF only reached the efficacy of PUI when NaOCl was heated up.

3D to 2D Magnetic Ordering of Fe3+ Oxides Induced by Their Layered Perovskite Structure.

The antiferromagnetic behavior of Fe3+ oxides of composition RE1.2Ba1.2Ca0.6Fe3O8, RE2.2Ba3.2Ca2.6Fe8O21, and REBa2Ca2Fe5O13 (RE = Gd, Tb) is highly influenced by the type of oxygen polyhedron around the Fe3+ cations and their ordering, which is coupled with the layered RE/Ba/Ca arrangement within the perovskite-related structure. Determination of the magnetic structures reveals different magnetic moments associated with Fe3+ spins in the different oxygen polyhedra (octahedron, tetrahedron, and square pyramid). The structural aspects impact on the strength of the Fe-O-Fe superexchange interactions and, therefore, on the Néel temperature (TN) of the compounds. The oxides present an interesting transition from three-dimensional (3D) to two-dimensional (2D) magnetic behavior above TN. The 2D magnetic interactions are stronger within the FeO6 octahedra layers than in the FeO4 tetrahedra layers.

Efficacy of EDTA and HEDP Chelators in the Removal of Mature Biofilm of Enterococcus faecalis by PUI and XPF File Activation.

BACKGROUND: Biofilm removal from the root canal during endodontic treatment is necessary to prevent further complications. Irrigation is essential to success. Several irrigants have been proposed without a proper comparison. The aim of the study is to compare the antibacterial capacity of different activated irrigants using passive ultrasonic activation (PUI) or XP-Endo finisher (XPF). METHODS: A total of 100 instrumented teeth were incubated in an Eppendorf tube containing 0.5 McFarland of Enterococcus faecalis and incubated for 2 weeks at 37 °C. Roots were divided into 5 groups (n = 20) according to the irrigant type: ethylenediaminetetraacetic acid (EDTA) (17%), ethydronic acid (HEDP) (9%) mixed with 5.25% sodium hypochlorite (NaOCl), EDTA (17%) mixed with 5.25% NaOCl, PBS, and a control group. Each group was divided into two subgroups (n = 10): PUI and XPF. RESULTS: As compared to the untreated control group, the irrigators included in the study had a significant effect in bacteria reduction. The obtained results show HEDP to be the most effective irrigant, since no bacteria were recovered after treatment of this group, followed by EDTA mixed with NaOCl and, finally, the EDTA-irrigated group. CONCLUSIONS: HEDP is the best irrigating agent in combination with XPF or PUI file activation to eliminate bacteria in our experimental model.

Superior Performance as Cathode Material for Intermediate-Temperature Solid Oxide Fuel Cells of the Ruddlesden-Popper n = 2 Member Eu2SrCo0.50Fe1.50O7-δ with Low Cobalt Content.

The effects of the contents of iron and cobalt on the crystal structure, oxygen content, thermal expansion coefficient, and electrical-electrochemical properties of materials Eu2SrCoxFe2-xO7-δ (x = 0.50 and 1.00) are reported. These oxides are well-ordered new members of the Ruddlesden-Popper series (Eu,Sr)n+1(Co,Fe)nO3n+1 system with n = 2 as determined by selected area electron diffraction and high-resolution transmission electron microscopy and X-ray diffraction studies. The two materials are semiconductors of p-type, with much higher total conductivity under working conditions for the low cobalt compound, Eu2SrCo0.50Fe1.50O7-δ. Composite cathodes prepared with this oxide present much lower area-specific resistance values (0.08 Ω·cm2 at 973 K in air) than composites containing Eu2SrCo1.00Fe1.00O7-δ (1.15 Ω·cm2). This significant difference is related to the much higher total conductivity and a sufficiently high content of oxygen vacancies in the Fe-rich phase. The excellent electrochemical performance of Eu2SrCo0.50Fe1.50O7-δ with low cobalt content, which shows one of the lowest area-specific resistance reported so far for a Ruddlesden-Popper oxide, makes it a good candidate for application as a cathode material for solid oxide fuel cells at intermediate temperatures in real devices.

The Effects of Sr Content on the Performance of Nd1-xSrxCoO3-δ Air-Electrode Materials for Intermediate Temperature Solid Oxide Fuel Cells under Operational Conditions.

The potential of the perovskite system Nd1-xSrxCoO3-δ (x = 1/3 and 2/3) as cathode material for solid oxide fuel cells (SOFCs) has been investigated via detailed structural, electrical, and electrochemical characterization. The average structure of x = 1/3 is orthorhombic with a complex microstructure consisting of intergrown, adjacent, perpendicularly oriented domains. This orthorhombic symmetry remains throughout the temperature range 373-1073 K, as observed by neutron powder diffraction. A higher Sr content of x = 2/3 leads to stabilization of the cubic perovskite with a homogeneous microstructure and with a higher oxygen vacancy content and cobalt oxidation state than the orthorhombic phase at SOFC operation temperature. Both materials are p-type electronic conductors with high total conductivities of 690 and 1675 S·cm-1 at 473 K in air for x = 1/3 and 2/3, respectively. Under working conditions, both compounds exhibit similar electronic conductivities, since x = 2/3 loses more oxygen on heating than x = 1/3, associated with a greater loss of p-type charger carriers. However, composite cathodes prepared with Nd1/3Sr2/3CoO3-δ and Ce0.8Gd0.2O2-δ present lower ASR values (0.10 Ω·cm2 at 973 K in air) than composites prepared with Nd2/3Sr1/3CoO3-δ and Ce0.8Gd0.2O2-δ (0.34 Ω·cm2). The high activity for the oxygen electrochemical reaction at intermediate temperatures is likely attributable to a large disordered oxygen-vacancy concentration, resulting in a very promising SOFC cathode for real devices.

Unprecedented rock-salt ordering of A and B cations in the double perovskite Nd2-xCaxMgTiO6-δ and defect association.

The partial substitution of up to 5% Nd+3 by Ca+2 results in the oxide Nd1.90Ca0.10MgTiO5.94 that presents some remarkable structural features with a noticeable influence on its properties. In this oxide with a monoclinic perovskite-like structure and an octahedral tilting scheme (a-a-b+), both A- and B-ions are arranged in a rock-salt like manner, representing therefore the first example of a type of perovskite theoretically predicted. Besides this unprecedented arrangement of A- and B-ions, the oxygen vacancies created through doping with acceptor ions are trapped by association with the acceptor defects and hence the mobility of these vacancies is strongly limited. The oxygen conductivity of the substituted material is lower and the activation energy for oxygen motion is higher than those of the parent oxide, in which the concentration of anion vacancies is only due to intrinsic defects.

Novel Perovskite Materials for Thermal Water Splitting at Moderate Temperature.

Materials with the formula Sr2 CoNb1-x Tix O6-δ (x=1.00, 0.70; δ=number of oxygen vacancies) present a cubic perovskite-like structure. They are easily and reversibly reduced in N2 or Ar and re-oxidized in air upon heating. Oxidation by water (wet N2 ), involving splitting of water at a temperature as low as 700 °C, produces hydrogen. Both compounds displayed outstanding H2 production in the first thermochemical cycle, the Sr2 CoNb0.30 Ti0.70 O6-δ material retaining its outstanding performance upon cycling, whereas the hydrogen yield of the x=1 oxide showed a continuous decay. The retention of the materials' ability to promote water splitting correlated with their structural, chemical, and redox reversibility upon cycling. On reduction/oxidation, Co ions reversibly changed their oxidation state to compensate the release/recovery of oxygen in both compounds. However, in Sr2 CoTiO6-δ , two phases with different oxygen contents segregated, whereas in Sr2 CoNb0.30 Ti0.70 O6-δ this effect was not evident. Therefore, this latter material displayed a hydrogen production as high as 410 µmol H 2 g-1 perovskite after eight thermochemical cycles at 700 °C, which is among the highest ever reported, making this perovskite a promising candidate for thermosolar water splitting in real devices.

Structures, Phase Fields, and Mixed Protonic-Electronic Conductivity of Ba-Deficient, Pr-Substituted BaZr0.7Ce0.2Y0.1O3-δ.

The BaZr0.7Ce0.2Y0.1O3-δ-BaPrO3-δ perovskite system, of interest for high-temperature electrochemical applications involving mixed protonic-electronic conductivity, forms a solid-solution with a wide interval of Ba substoichiometry in the range Ba(Ce0.2Zr0.7)1- xPr xY0.1O3-δ, 0 ≤ x ≤ 1. Structural phase transitions mapped as a function of temperature and composition by high-resolution neutron powder diffraction and synchrotron X-ray diffraction reveal higher symmetry for lower Pr content and higher temperatures, with the largest stability field observed for rhombohedral symmetry (space group, R3̅ c). Rietveld refinement, supported by magnetic-susceptibility measurements, indicates that partitioning of the B-site cations over the A and B perovskite sites compensates Ba substoichiometry in preference to A-site vacancy formation and that multiple cations are distributed over both sites. Electron-hole transport dominates electrical conductivity in both wet and dry oxidizing conditions, with total conductivity reaching a value of ∼0.5 S cm-1 for the x = 1 end-member in dry air at 1173 K. Higher electrical conductivity and the displacement of oxygen loss to higher temperatures with increasing Pr content both reflect the role of Pr in promoting hole formation at the expense of oxygen vacancies. In more reducing conditions (N2) and at low Pr contents, conductivity is higher in humidified atmospheres (∼0.023 atm pH2O) indicating a protonic contribution to transport, whereas the greater electron-hole conductivity with increasing Pr content results in lower conductivity in humidified N2 due to the creation of protonic defects and the consumption of holes.

A Critical Review of Existing Criteria for the Prediction of Pyrochlore Formation and Stability.

Depending on intrinsic (e.g., radius ratio rule rLn/ rZr) and extrinsic factors (e.g., processing conditions), pyrochlore-type Ln2Zr2O7 oxides achieve variable degrees of structural disorder. We report on a systematic study of the structural and microstructural characteristics of the Gd2- xLn xZr2O7 system, exploring the effect of replacing Gd with a wide range of homovalent lanthanide ions (Ln = Nd, Sm, Dy, Ho, Y, and Er; x = 0.20 and 0.80). All compositions were prepared via a mechanochemical reaction between the corresponding oxides and characterized by X-ray diffraction (standard and synchrotron sources) using the Rietveld method, as well as by Raman spectroscopy. Irrespective of chemical composition, this study reveals that all compositions exhibit a fluorite-like structure. Furthermore, by firing each sample at 800 and 1400 °C, we are able to analyze the transition to pyrochlore-like structures, featuring different degrees of disorder, in all but Gd1.20Y0.80Zr2O7, which retains the fluorite structure even after heating. The structural data are used to assess the existing criteria for predicting the formation and stability of the pyrochlore structure; according to this analysis, the simple radius ratio rule ( rLn/ rZr), provides a useful and sufficiently robust criterion. Because the pyrochlore structure has a strong tendency to disorder, it is not possible to define an empirical index similar to the Goldschmidt tolerance factor for perovskite.

Structure and Electrical-Transport Relations in Ba(Zr,Pr)O3-δ Perovskites.

Members of the perovskite solid solution BaZr1-xPrxO3-δ (0.2 ≤ x ≤ 0.8) with potential high-temperature electrochemical applications were synthesized via mechanical activation and high-temperature annealing at 1250 °C. Structural properties were examined by Rietveld analysis of neutron powder diffraction and Raman spectroscopy at room temperature, indicating rhombohedral symmetry (space group R3̅c) for members x = 0.2 and 0.4 and orthorhombic symmetry (Imma) for x = 0.6 and 0.8. The sequence of phase transitions for the complete solid solution from BaZrO3 to BaPrO3 is Pm3̅m → R3̅c → Imma → Pnma. The structural data indicate that Pr principally exists as Pr4+ on the B site and that oxygen content increases with higher Pr content. Electrical-conductivity measurements in the temperature range of 250-900 °C in dry and humidified (pH2O ≈ 0.03 atm) N2 and O2 atmospheres revealed an increase of total conductivity by over 2 orders of magnitude in dry conditions from x = 0.2 to x = 0.8 (σ ≈ 0.08 S cm-1 at 920 °C in dry O2 for x = 0.8). The conductivity for Pr contents x > 0.2 is attributable to positively charged electronic carriers, whereas for x = 0.2 transport in dry conditions is n-type. The change in conduction mechanism with composition is proposed to arise from the compensation regime for minor amounts of BaO loss changing from predominantly partitioning of Pr on the A site to vacancy formation with increasing Pr content. Conductivity is lower in wet conditions for x > 0.2 indicating that the positive defects are, to a large extent, charge compensated by less mobile protonic species. In contrast, the transport mechanism of the Zr-rich composition (x = 0.2), with much lower electronic conductivity, is essentially independent of moisture content.

Defect Chemistry, Electrical Properties, and Evaluation of New Oxides Sr2 CoNb1-x Tix O6-δ (0≤x≤1) as Cathode Materials for Solid Oxide Fuel Cells.

The perovskite series Sr2 CoNb1-x Tix O6-δ (0≤x≤1) was investigated in the full compositional range to assess its potential as cathode material for solid oxide fuel cell (SOFC). The variation of transport properties and thus, the area specific resistances (ASR) are explained by a detailed investigation of the defect chemistry. Increasing the titanium content from x=0-1 produces both oxidation of Co3+ to Co4+ (from 0 up to 40 %) and oxygen vacancies (from 6.0 to 5.7 oxygen atom/formula unit), although each charge compensation mechanism predominates in different compositional ranges. Neutron diffraction reveals that samples with high Ti-contents lose a significant amount of oxygen upon heating above 600 K. Oxygen is partially recovered upon cooling as the oxygen release and uptake show noticeably different kinetics. The complex defect chemistry of these compounds, together with the compositional changes upon heating/cooling cycles and atmospheres, produce a complicated behavior of electrical conductivity. Cathodes containing Sr2 CoTiO6-δ display low ASR values, 0,13â€…Ω cm2 at 973 K, comparable to those of the best compounds reported so far, being a very promising cathode material for SOFC.

Effect of Internal Pressure and Temperature on Phase Transitions in Perovskite Oxides: The Case of the Solid Oxide Fuel Cell Cathode Materials of the La2-xSrxCoTiO6 Series.

The symmetry of the room-temperature (RT) structure of title compounds La2-xSrxCoTiO6-δ changes with x, from P21/n (0 ≤ x ≤ 0.2) to Pnma (0.3 ≤ x ≤ 0.5) and to R3̅c (0.6 ≤ x ≤ 1). For x = 1 the three pseudocubic cell parameters become very close suggesting a transition to a cubic structure for higher Sr contents. Similar phase transitions were expected to occur on heating, paralleling the effect of internal pressure induced by substitution of La3+ by Sr2+. However, only some of these aforementioned transitions have been thermally induced. The symmetry-adapted modes formalism is used in the structural refinements and fitting of neutron diffraction data recorded from RT to 1273 K. Thus, for x = 1, the out-of-phase tilting of the BO6 octahedra vanishes progressively on heating, and a cubic structure with Pm3̅m symmetry is found at 1073 K. For lower Sr contents this transition is predicted to occur far above the temperature limit of common experimental setups. The analysis of the evolution of the perovskite tolerance factor, t-factor, with both Sr content and temperature indicates that temperature has a limited ability to release structural stress and thus to enable transitions to more symmetric phases. This is particularly true when compared to the effect of internal pressure induced by substitution of La by Sr. The existence of phase transitions in materials for solid oxide fuel cells that are usually exposed to heating-cooling cycles may have a detrimental effect. This work suggests strategies to stabilize the high-symmetry high-temperature phase of perovskite oxides through internal-pressure chemically induced.

Synthesis and characterization of NaNiF3·3H2O: an unusual ordered variant of the ReO3 type.

A new hydrated sodium nickel fluoride with nominal composition NaNiF3·3H2O was synthesized using an aqueous solution route. Its structure was solved by means of ab initio methods from powder X-ray diffraction and neutron diffraction data. NaNiF3·3H2O crystallizes in the cubic crystal system, space group Pn3̅ with a = 7.91968(4) Å. The framework, derived from the ReO3 structure type, is built from NaX6 and NiX6 (X = O, F) corner-shared octahedra, in which F and O atoms are randomly distributed on a single anion site. The 2a × 2a × 2a superstructure arises from the strict alternate three-dimensional linking of NaX6 and NiX6 octahedra together with the simultaneous tilts of the octahedra from the cube axis (φ = 31.1°), with a significant participation of hydrogen bonding. NaNiF3·3H2O corresponds to a fully cation-ordered variant of the In(OH)3 structure, easily recognizable when formulated as NaNi(XH)6 (X = O, F). It constitutes one of the rare examples for the a(+)a(+)a(+) tilting scheme with 1:1 cation ordering in perovskite-related compounds. The Curie-like magnetic behavior well-reflects the isolated paramagnetic Ni(2+) centers without worth mentioning interactions. While X-ray and neutron diffraction data evidence Na/Ni order in combination with O/F disorder as a main feature of this fluoride, results from Raman and magic-angle spinning NMR spectroscopies support the existence of specific anion arrangements in isolated square windows identified in structural refinements. In particular, formation of water molecules derives from unfavorable FH bond formation.

Synthesis of a 12R-type hexagonal perovskite solid solution Sr3NdNb(3-x)Ti(x)O(12-δ) and the influence of acceptor doping on electrical properties.

A solid solution forms for Sr3NdNb(3-x)Ti(x)O(12-δ) with approximate limits 0 ≤ x ≤ 0.06. The system crystallizes with a 12R-type hexagonal perovskite structure in the space group R3, as determined by neutron diffraction and selected area electron diffraction. The electrical properties of the end members have been investigated by impedance spectroscopy in the temperature range 550-800 °C under various gas atmospheres and as a function of oxygen and water-vapour partial pressure. Proton transport dominates under wet oxidising conditions in the temperature range 550-700 °C, as confirmed by the H(+)/D(+) isotope effect. Acceptor doping considerably enhances proton conductivity with a value of 3.3 × 10(-6) S cm(-1) for the bulk response of x = 0.06 at 700 °C in moistened air. The presence of a -» slope for both doped and undoped samples in the range 10(-19) ≤ pO2 ≤ 10(-8) atm at 900 °C indicates n-type transport under reducing conditions following the extrinsic model attributable to acceptor centres. The conductivity is essentially independent of pO2 at 600 °C under dry oxidising conditions, consistent with oxide-ion transport; a positive power-law dependence at higher temperature indicates extrinsic behaviour and a significant electron-hole contribution. The dielectric constant at RT of nominally stoichiometric Sr3NdNb3O12 is εr ∼ 37, with a moderately high quality factor of Q × f ∼ 16,400 GHz at fr ∼ 6.4 GHz. The temperature coefficient of resonant frequency of x = 0 is τf ∼ 12 ppm °C(-1), which lowers to -3 ppm °C(-1) for the Ti-doped phase x = 0.06.

Complex magnetic behaviour of Sr2CoNb1-xTixO6 (0 ≤ x ≤ 0.5) as a result of a flexible microstructure.

We report the rich magnetic behaviour of Sr2CoNb1-xTixO6 (0 ≤ x ≤ 0.5) oxides as a result of their complex microstructure. Although these oxides show an average simple-cubic perovskite structure, they present a flexible microstructure due to short-range ordering between Co/Ti and Nb cations in the perovskite B-sites. The microstructure consists of double-cubic perovskite domains grown in a simple-cubic perovskite matrix. The size and number of the double-cubic perovskite domains decrease as the Ti content increases. As a result of aliovalent substitution of Nb(5+) by Ti(4+) in the parent Sr2CoNbO6 mixed-valence Co(3+)/Co(4+) oxides are obtained. A spin glass-like state has been observed at low temperatures for all the series, with freezing temperatures increasing with the Ti-content in the range 22 to 33 K. Furthermore, the x = 0.3 and x = 0.5 samples show non-interacting superparamagnetic particle-like dynamics associated with relatively high amounts of Co(4+), with "blocking temperatures" of 13 and ∼16 K, respectively. The complex magnetic behaviour of the title oxides seems to be connected with the clustering of magnetic Co(3+) and the distribution of Co(4+) as a result of the microstructure.

Microwave-assisted synthesis, microstructure, and physical properties of rare-earth chromites.

The full rare-earth (RE) chromites series (RE)CrO(3) with an orthorhombic distorted (Pnma) perovskite structure and the isostructural compound YCrO(3) can be synthesized through a simple microwave-assisted technique, yielding high-quality materials. Magnetization measurements evidence that the Néel temperature for antiferromagnetic Cr(3+)-Cr(3+) ordering strongly depends on the RE(3+) ionic radius (IOR), and a rich variety of different magnetic spin interactions exists. Dielectric spectroscopy on sintered pellets indicates electronic inhomogeneity in all samples as manifested by the presence of at least two dielectric relaxation processes associated with grain boundary and grain interior bulk contributions. X-ray diffraction, Raman spectroscopy, and temperature-dependent dielectric permittivity data do not indicate potential noncentrosymmetry in the crystal or concomitant ferroelectricity. Strong correlations between the magnetic and dielectric properties were not encountered, and microwave-synthesized (RE)CrO(3) may not be classified as magnetoelectric or multiferroic materials.

New perovskite materials of the La(2-x)Sr(x)CoTiO6 series.

Substitution of La(3+) by Sr(2+) in the double perovskite La(2)CoTiO(6) yields materials of the La(2-x)Sr(x)CoTiO(6) series showing a significant amount of trivalent cobalt ions when prepared at ambient atmosphere. The as-prepared compounds can be reduced in severe conditions retaining the perovskite structure while inducing the formation of a large amount of oxygen vacancies. The limit of aliovalent substitution in this series was found to extend up to x = 1. For substitution of La(3+) up to 15% cobalt and titanium are ordered, though the order is progressively lost as x increases; for x≥ 0.30 no ordering is observed as evidenced by magnetic measurements. The ability of these materials to present either cobalt ions in a mixed oxidation state or large amounts of anion vacancies depending on the atmosphere makes them interesting to be further investigated regarding their electrical and electrochemical properties, and hence, their usefulness in some electrochemical devices.

Insight into ramsdellite LI(2)Ti(3)O(7) and its proton-exchange derivative.

Despite being proven to be a good lithium-ion conductor 30 years ago, the crystal structure of the ramsdellite-like Li(2)Ti(3)O(7) has remained uncertain, with two potential models for locating the lithium ions in the structure. Although the model presently accepted states that both lithium and titanium occupy the octahedral sites in the framework, evidence against this model are provided by (6)Li and (7)Li MAS NMR spectroscopy. Thus, about 14% of these octahedral positions are empty since no lithium in octahedral coordination is present in the material. When Li(2)Ti(3)O(7)-ramsdellite is treated with nitric acid a complete exchange of lithium by protons is produced to yield H(2)Ti(3)O(7). The crystal structure of this proton-exchanged ramsdellite has been re-examined combining X-ray diffraction (XRD), neutron powder diffraction (NPD), and spectroscopic ((1)H and (7)Li MAS NMR) techniques. Two kinds of protons are present in this material with different acidity because of the local environments of oxygen atoms to which protons are bonded, namely, low acidic protons strongly bonded to highly charged oxygen atoms (coordinated to two Ti(4+) and a vacancy); and protons linked to low charged oxygen atoms (bonded to three Ti(4+) ions) which will display a more acidic behavior. H(2)Ti(3)O(7) absorbs water; proton mobility is enhanced by the presence of absorbed water, giving rise to a large improvement of its electrical conductivity in wet atmospheres. Thus, it seems that water molecules enter the tunnels in the structure providing a vehicle mechanism for proton diffusion.

Structural characterization and NMR study of NaNbWO(6) and its proton-exchanged derivatives.

The structural characterization of NaNbWO(6), prepared by the ceramic route, has been performed. Electron diffraction has shown the presence of two related phases in a 1:1 ratio, whose lattice parameters correspond to those of the well-known tetragonal tungsten bronzes (TTB) and those of a monoclinically distorted phase. In addition to basic unit cells, the morphology of the two phases has been found to be similar, but they present a slight difference in the W/Nb ratio. (1)H and (23)Na magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectra of NaNbWO(6) and its proton-exchanged derivatives have been interpreted on the basis of the ideal TTB structure. The average structure and the morphology remain unchanged in Na(1-x)H(x)NbWO(6) derivatives. (1)H and (23)Na MAS-NMR spectroscopies have been used to monitor changes produced during exchange processes. It has been shown that the exchange of Na ions is mainly produced, but not exclusively, at tetragonal channels. However, a large amount of Na ions at the pentagonal channels do not exchange with protons, suggesting that these ions are needed to stabilize the TTB-like structure. A tentative distribution of sodium ions in the most-exchanged oxide, deduced from NMR results, approximately (Na(0.46))(p)(Na(0.08))(s)H(0.46)NbWO(6), has been proposed. NMR spectra of Na(1-x)H(x)NbWO(6) indicate that two different OH groups are formed upon exchanging. The study of samples hydrated with D(2)O allowed us to conclude that deuterons of adsorbed water exchange with protons of the two OH groups. The proton-deuteron exchange is slow at room temperature but is strongly enhanced at 90 degrees C. This observation relates to the proton conductivity displayed by exchanged products under a humid atmosphere.