Structure, electrical conductivity and oxygen transport properties of perovskite-type oxides CaMn1-x-yTixFeyO3-δ.

Calcium manganite-based perovskite-type oxides hold promise for application in chemical looping combustion processes and oxygen transport membranes. In this study, we have investigated the structure, electrical conductivity and oxygen transport properties of perovskite-type oxides CaMn1-x-yTixFeyO3-δ. Distinct from previous work, data of high-temperature X-ray diffraction (HT-XRD) in the temperature range 600-1000 °C (with intervals of 25 °C) demonstrates that CaMnO3-δ (CM) transforms from orthorhombic to a mixture of orthorhombic and tetragonal phases between 875 °C and 900 °C. Rietveld refinements show the formation of a pure tetragonal phase at 975 °C and of a pure cubic phase at 1000 °C. Partial substitution of manganese by iron and/or titanium to yield CaMn0.875Ti0.125O3-δ (CMT), CaMn0.85Fe0.15O3-δ (CMF) or CaMn0.725Ti0.125Fe0.15O3-δ (CMTF) leads to different phase behaviours. While CMT remains orthorhombic up to the highest temperature covered by the HT-XRD experiments, CMF and CMTF undergo an orthorhombic → tetragonal → cubic sequence of phase transitions. Electrical conductivity relaxation measurements are conducted to determine the chemical diffusion coefficient (Dchem) and the surface exchange coefficient (kchem) of the materials. The results demonstrate that oxygen transport is hindered in the tetragonal phase, when occurring, which is attributed to a possible ordering of oxygen vacancies. The small polaron electrical conductivity of CM in the cited temperature range is lowered upon partial manganese substitution, by about 10% for CMF and up to half an order of magnitude for CMT and CMTF.

Ammonia and methane emissions from small herd cattle buildings in a cold climate.

Ammonia (NH3) and methane (CH4) emission measurements that reflect local production conditions are required to track progress in national emission policies and verify emission factors. The findings can also be used to better understand key factors influencing emissions. This is especially important in Norway, which has long cold winters, and small cattle herds in mechanically ventilated buildings. However, until now, NH3 and CH4 emissions from Norwegian cattle buildings have not been reported in literature. Moreover, in other cold climates, NH3 and CH4 emissions are often taken from large dairy herds in naturally ventilated buildings, with less focus on suckler cows. The objectives were to assess indoor climate, report NH3 and CH4 emissions and examine the impact of climatic factors on NH3 and CH4 emissions in three small herd dairy and suckler cow buildings over three seasons. Three of the buildings had mechanical ventilation, while one was naturally ventilated. The suckler building had higher relative humidity (RH > 90 %) and NH3 concentrations (> 25 ppm) due to lower minimum air change rate (ACH = 1.2 h-1). The suckler building also had the highest NH3 emissions (2.04 g Livestock Unit (LU)-1 h-1) followed by the mechanically ventilated dairy building (1.92 g LU-1 h-1) with the highest ACH. These two buildings had the lowest stocking densities and floor areas. In contrast, the suckler building had the lowest CH4 emissions (6.8-10.7 g LU-1 h-1). Methane emissions from the dairy building with the supply-exhaust air mixing system (16.4-19.3 g LU-1 h-1) was higher than the other dairy buildings (11.7-13.8 g LU-1 h-1). Temperature influenced NH3 emissions however, the direction of association between temperature and NH3 emissions differed among buildings. Relationship between RH and NH3 emissions was positive, but the correlation coefficient (R2 = 0.67) was strongest in the building with the highest RH.

Investigation of La1-xSrxCrO3-∂ (x ~ 0.1) as Membrane for Hydrogen Production.

Various inorganic membranes have demonstrated good capability to separate hydrogen from other gases at elevated temperatures. Hydrogen-permeable, dense, mixed proton-electron conducting ceramic oxides offer superior selectivity and thermal stability, but chemically robust candidates with higher ambipolar protonic and electronic conductivity are needed. In this work, we present for the first time the results of various investigations of La1-xSrxCrO3-∂ membranes for hydrogen production. We aim in particular to elucidate the material's complex transport properties, involving co-ionic transport of oxide ions and protons, in addition to electron holes. This opens some new possibilities for efficient heat and mass transfer management in the production of hydrogen. Conductivity measurements as a function of pH2 at constant pO2 exhibit changes that reveal a significant hydration and presence of protons. The flux and production of hydrogen have been measured under different chemical gradients. In particular, the effect of water vapor in the feed and permeate gas stream sides was investigated with the aim of quantifying the ratio of hydrogen production by hydrogen flux from feed to permeate and oxygen flux the opposite way ("water splitting"). Deuterium labeling was used to unambiguously prove flux of hydrogen species.

Hydrogen in oxides.

The paper reviews the history and present understanding of protons in oxides; their defect chemistry, thermodynamics, and transport. Focus is put on correlations between hydration thermodynamics and other materials properties which may help to predict proton uptake and proton conduction in oxides. Also effects of defect association and the particular problem of high grain boundary resistance in high temperature proton conductors are addressed. In the second part, a number of experimental observations attributed to the presence of hydride ions under mildly reducing conditions are discussed in relation to the unlikelihood that general thermodynamic considerations predict of finding these species under such conditions.