An electron hole doping and soft x-ray spectroscopy study on La1-xSrxFe0.75Ni0.25O3-{\delta}

The conductivity of the electron hole and polaron conductor La1-xSrxFe0.75Ni0.25O3-{\delta}, a potential cathode material for intermediate temperature solid oxide fuel cells, was studied for 0 <x < 1 and for temperatures 300 K <T < 1250 K. In LaSrFe-oxide, an ABO3 type perovskite, A-site substitu-tion of the trivalent La3+ by the divalent Sr2+ causes oxidation of Fe3+ towards Fe4+, which forms conducting electron holes. Here we have in addition a B-site substitution by Ni. The compound for x = 0.5 is identified as the one with the highest conductivity ({\sigma} ~ 678 S/cm) and lowest activation energy for polaron conductivity (Ep = 39 meV). The evolution of the electronic structure was monitored by soft x-ray Fe and oxygen K-edge spectroscopy. Homogeneous trend for the oxida-tion state of the Fe was observed. The variation of the ambient temperature conductivity and activation energy with relative Sr content (x) shows a correlation with the ratio of (eg/eg+t2g) in Fe L3 edge up to x=0.5. The hole doping process is reflected by an almost linear trend by the variation of the pre-peaks of the oxygen K-edge soft x-ray absorption spectra

Energy separation in oscillatory Hamiltonian systems without any non-resonance condition

We consider multiscale Hamiltonian systems in which harmonic oscillators with several high frequencies are coupled to a slow system. It is shown that the oscillatory energy is nearly preserved over long times eps^{-N} for arbitrary N>1, where eps^{-1} is the size of the smallest high frequency. The result is uniform in the frequencies and does not require non-resonance conditions.Comment: 13 page

Correlation of conductivity and angle integrated valence band photoemission characteristics in single crystal iron perovskites for 300 K < T < 800 K: Comparison of surface and bulk sensitive methods

A single crystal monolith of La0.9Sr0.1FeO3 and thin pulsed laser deposited film of La0.8Sr0.2Fe0.8Ni0.2O3 were subject to angle integrated valence band photoemission spectroscopy in ultra high vacuum and conductivity experiments in ambient air at temperatures from 300 K to 800 K. Except for several sputtering and annealing cycles, the specimen were not prepared in-situ.. Peculiar changes in the temperature dependent, bulk representative conductivity profile as a result of reversible phase transitions, and irreversible chemical changes are semi-quantitatively reflected by the intensity variation in the more surface representative valence band spectra near the Fermi energy. X-ray photoelectron diffraction images reflect the symmetry as expected from bulk iron perovskites. The correlation of spectral details in the valence band photoemission spectra (VB PES) and details of the conductivity during temperature variation suggest that valuable information on electronic structure and transport properties of complex materials may be obtained without in-situ preparation

High temperature oxygen NEXAFS valence band spectra and conductivity of LaFe3/4Ni1/4O3 from 300 K to 773 K

LaFe3/4Ni1/4O3 was subjected to oxygen near edge x-ray absorption fine structure (NEXAFS) spectroscopy for 300 K < T < 773 K. The spectra show in the pre-edge a small hole doped peak originating from Ni substitution. The relative spectral weight of this transition to the weight of the hybridized O(2p) - Fe(3d) transitions scales with T and has a maximum at around 600 K. The characteristic energies of the thermal activated spectral intensity and conductivity suggest that the concentration of charge transferred electrons from O(2p) to Ni(3d) increases and that the pre-edges account in part for the polaron activated transport

Effect of intergranular glass films on the electrical conductivity of 3Y-TZP

The electrical conductivity of 3Y-TZP ceramics containing SiO2 and Al2O3 has been investigated by complex impedance spectroscopy between 500 and 1270 K. At low temperatures, the total electrical conductivity is suppressed by the grain boundary glass films. The equilibrium thickness of intergranular films is 1-2 nm, as derived using the "brick-layer” model and measured by HRTEM. A change in the slope of the conductivity Arrhenius plots occurs at the characteristic temperature Tb at which the macroscopic grain boundary resistivity has the same value as the resistivity of the grains. The temperature dependence of the conductivity is discussed in terms of a series combination of RC element

Entanglement of charge transfer, hole doping, exchange interaction and octahedron tilting angle and their influence on the conductivity of La1-xSrxFe0.75Ni0.25O3-{\delta}: A combination of x-ray spectroscopy and diffraction

Substitution of La by Sr in the 25% Ni doped charge transfer insulator LaFeO3 creates structural changes that inflect the electrical conductivity caused by small polaron hopping via exchange interactions and charge transfer. The substitution forms electron holes and a structural crossover from orthorhombic to rhombohedral symmetry, and then to cubic symmetry. The structural crossover is accompanied by a crossover from Fe3+-O2--Fe3+ superexchange interaction to Fe3+-O2--Fe4+ double exchange interaction, as evidenced by a considerable increase of conductivity. These interactions and charge transfer mechanism depend on superexchange angle, which approaches 180{\deg} upon increasing Sr concentration, leading an increased overlap between the O (2p) and Fe/Ni (3d) orbitals

Redistribution of Aluminum Ions During Processing of Sialon Ceramics

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65916/1/j.1151-2916.1986.tb04820.x.pd

Insolubility of Mg in Β-Si 3 N 4 in the System Al-Mg-Si-O-N

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65816/1/j.1151-2916.1978.tb09345.x.pd

On the Nonlinear Stability of Asymptotically Anti-de Sitter Solutions

Despite the recent evidence that anti-de Sitter spacetime is nonlinearly unstable, we argue that many asymptotically anti-de Sitter solutions are nonlinearly stable. This includes geons, boson stars, and black holes. As part of our argument, we calculate the frequencies of long-lived gravitational quasinormal modes of AdS black holes in various dimensions. We also discuss a new class of asymptotically anti-de Sitter solutions describing noncoalescing black hole binaries.Comment: 26 pages. 5 figure

Microstructure and Mechanical Properties of the in situ Β-Si 3 N 4 /Α′-SiAlON Composite

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65911/1/j.1151-2916.1994.tb04604.x.pd