Investigation into the effect of Y, Yb doping in Ba2In2O5: determination of the solid solution range and co-doping with phosphate

In this paper we examine the effect of Y, Yb doping in Ba2In2O5, examining the solid solution range and effect on the conductivity and CO2 stability. The results showed that up to 35% Y, Yb can be introduced, and this doping leads to an introduction of disorder on the oxygen sublattice, and a corresponding increase in conductivity. Further increases in Y, Yb content could be achieved through co-doping with phosphate. While this co-doping strategy led to a reduction in the conductivity, it did have a beneficial effect on the CO2 stability, and further improvements in the CO2 stability could be achieved through La and P co-doping

Synthesis and characterization of oxyanion (phosphate, sulfate) doped Ba2_2Sc2_2−_-y_yGay_yO5_5

In this paper we examine the effect of partial substitution of Ga for Sc in the oxyanion (phosphate, sulfate) containing perovskites, Ba2Sc$_2$$_-$$_x$P$_x$O$_5$$_+$$_x$ and Ba$_2$S$_c$$_2$$_-$$_x$S$_x$O$_5$$_+$3$_x$$_/$$_2$ with the samples analysed through a combination of X-ray diffraction, TGA, Raman spectroscopy and conductivity measurements. The results demonstrate that in both cases, Ga can be incorporated in place of Sc up to 40%. In order to accommodate the increasing Ga content, a reduction in the oxyanion content is required. Thus for the highest Ga content sample achieved, only 10% oxyanion incorporation was achieved giving endmember compositions of Ba$_2$S$_c$Ga$_0$$_.$$_8$P$_0$$_.$$_2$O$_5$$_.$$_2$ and Ba$_2$S$_c$Ga$_0$$_.$$_8$S$_0$$_.$$_2$O$_5$$_.$$_3$ for phosphate and sulfate doping respectively. While the Ga doping was shown to significantly improve the stability of the systems towards CO$_2$ containing atmospheres, conductivity measurements showed a reduction in the conductivity with increasing Ga content

New electrolyte materials for solid oxide fuel cells

Two general systems, brownmillerite-type Ba$_2$In$_2$O$_5$ and apatite-type silicates have been investigated for potential solid oxide fuel cell electrolyte applications. The combination of powder diffraction, NMR, TGA, Raman and AC impedance spectroscopy indicated the successful incorporation of phosphate, sulphate and silicate into the Ba$_2$In$_2$O$_5$ structure leading to a transition from an ordered brownmillerite-type structure to a disordered perovskite-type, which led to the conductivity enhancement below 800 °C, along with a significant protonic contribution in wet atmospheres. The CO$_2$ stability was also shown to be improved on doping. This oxyanion doping strategy has been extended to the analogous system, Ba$_2$Sc$_2$O$_5$, which resulted in samples with high conductivity and good stability towards CO$_2$. Neutron diffraction studies on La$_9$$_.$$_6$Si$_6$O$_2$$_6$$_.$$_4$ indicated that the interstitial oxide ion is located near the channel centre. Further interstitial anions could be accommodated through hydration, which led to displacement of the interstitial site away from the channel centre, with an accompanying swelling of the channel. Although long term annealing of these apatite silicates showed no apparent significant structural change, a reduction in the bulk conductivity was observed, while the grain boundary conductivity was improved, thus resulting in a small enhancement in the total conductivity below 400 °C

Oxyanion doping strategies to enhance the ionic conductivity in Ba2In2O5

In this paper we report the successful incorporation of phosphate and sulphate groups into the ionic conductor, Ba2In2O5, with the samples analysed through a combination of X-ray diffraction, NMR, TGA, Raman spectroscopy and conductivity measurements. The results show that such oxyanion incorporation leads to a conversion from an ordered brownmillerite-type structure to a disordered perovskite-type, and hence increases the conductivity at temperatures < 800○C. In wet atmospheres, there is evidence for a significant enhancement of the conductivity through a protonic contribution.\u

Synthesis and characterization of proton conducting oxyanion doped Ba2Sc2O5

In this paper we report the successful synthesis of the cubic oxyanion containing perovskites, Ba2Sc2-xPxO5+x (x=0.4, 0.5), with the samples analysed through a combination of X-ray diffraction, NMR, TGA, Raman spectroscopy and conductivity measurements. Conductivity measurements indicate a p-type contribution to the conductivity in oxidizing conditions at elevated temperatures, with evidence for proton conduction in wet atmospheres. For the latter bulk conductivities of 5.9 x 10-3 and 1.3 x 10-3 Scm-1 at 500○C were obtained for x=0.4 and 0.5 respectively, comparable to other perovskite proton conductors, while the stability towards CO2 containing atmospheres was improved compared to BaCeO3 based systems.\ud Related Si doped systems have also been prepared, although in this case small Ba2SiO4 impurities are observed. We also provide evidence to suggest that “undoped” Ba2Sc2O5 contains carbonate groups, which accounts for its thermal instability

Aggressive Regimens for Multidrug-Resistant Tuberculosis Decrease All-Cause Mortality

Rationale: A better understanding of the composition of optimal treatment regimens for multidrug-resistant tuberculosis (MDR-TB) is essential for expanding universal access to effective treatment and for developing new therapies for MDR-TB. Analysis of observational data may inform the definition of an optimized regimen. Objectives: This study assessed the impact of an aggressive regimen–one containing at least five likely effective drugs, including a fluoroquinolone and injectable–on treatment outcomes in a large MDR-TB patient cohort. Methods: This was a retrospective cohort study of patients treated in a national outpatient program in Peru between 1999 and 2002. We examined the association between receiving an aggressive regimen and the rate of death. Measurements and Main Results: In total, 669 patients were treated with individualized regimens for laboratory-confirmed MDR-TB. Isolates were resistant to a mean of 5.4 (SD 1.7) drugs. Cure or completion was achieved in 66.1% (442) of patients; death occurred in 20.8% (139). Patients who received an aggressive regimen were less likely to die (crude hazard ratio [HR]: 0.62; 95% CI: 0.44,0.89), compared to those who did not receive such a regimen. This association held in analyses adjusted for comorbidities and indicators of severity (adjusted HR: 0.63; 95% CI: 0.43,0.93). Conclusions: The aggressive regimen is a robust predictor of MDR-TB treatment outcome. TB policy makers and program directors should consider this standard as they design and implement regimens for patients with drug-resistant disease. Furthermore, the aggressive regimen should be considered the standard background regimen when designing randomized trials of treatment for drug-resistant TB

Lithium Transport in Li4.4M0.4M ' S-0.6(4) (M = Al3+, Ga3+, and M ' = Ge4+, Sn4+): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies

In order to understand the structural and compositional factors controlling lithium transport in sulfides, we explored the Li5AlS4 – Li4GeS4 phase field for new materials. Both parent compounds are defined structurally by a hexagonal close packed sulfide lattice, where distinct arrangements of tetrahedral metal sites give Li5AlS4 a layered structure and Li4GeS4 a three dimensional structure related to γ-Li3PO4. The combination of the two distinct structural motifs is expected to lead to new structural chemistry. We identified the new crystalline phase Li4.4Al0.4Ge0.6S4, and investigated the structure and Li+ ion dynamics of the family of structurally related materials Li4.4M0.4M’0.6S4 (M= Al3+, Ga3+ and M’= Ge4+, Sn4+). We used neutron diffraction to solve the full structures of the Al-homologues, which adopt a layered close-packed structure with a new arrangement of tetrahedral (M/M’) sites and a novel combination of ordered and disordered lithium vacancies. AC impedance spectroscopy revealed lithium conductivities in the range 3(2) x 10-6 to 4.3(3) x 10-5 S cm-1 at room temperature with activation energies between 0.43(1) and 0.38(1) eV. Electrochemical performance was tested in a plating and stripping experiment against Li metal electrodes and showed good stability of the Li4.4Al0.4Ge0.6S4 phase over 200 hours. A combination of variable temperature 7Li solid state nuclear magnetic resonance spectroscopy and ab initio molecular dynamics calculations on selected phases showed that two dimensional diffusion with a low energy barrier of 0.17 eV is responsible for long-range lithium transport, with diffusion pathways mediated by the disordered vacancies while the ordered vacancies do not contribute to the conductivity. This new structural family of sulfide Li+ ion conductors offers insight into the role of disordered vacancies on Li+ ion conductivity mechanisms in hexagonally close packed sulfides that can inform future materials design