Ionic conductivity of nanocrystalline yttria-stabilized zirconia: Grain boundary and size effects

9 páginas, 6 figuras, 3 tablas.-- PACS number(s): 66.30.H-.-- et al.We report on the effect of grain size on the ionic conductivity of yttria-stabilized zirconia samples synthesized by ball milling. Complex impedance measurements, as a function of temperature and frequency are performed on 10 mol % yttria-stabilized zirconia nanocrystalline samples with grain sizes ranging from 900 to 17 nm. Bulk ionic conductivity decreases dramatically for grain sizes below 100 nm, although its activation energy is essentially independent of grain size. The results are interpreted in terms of a space-charge layer resulting from segregation of mobile oxygen vacancies to the grain-boundary core. The thickness of this space-charge layer formed at the grain boundaries is on the order of 1 nm for large micron-sized grains but extends up to 7 nm when decreasing the grain size down to 17 nm. This gives rise to oxygen vacancies depletion over a large volume fraction of the grain and consequently to a significant decrease in oxide-ion conductivity.We acknowledge financial support by Junta de Comunidades de Castilla-La Mancha through Project No. PAI-05-013, by CAM under Grant No. S2009/MAT-1756 (Phama), by Spanish MICINN through Grants No. MAT2008-06517-C02, No. MAT2008-06542-C04, and No. FIS2009-12964- C05-04, and Consolider Ingenio 2010 under Grant No. CSD2009-00013 (Imagine).Peer reviewe

Ab initio x-ray absorption study of copper K -edge XANES spectra in Cu(II) compounds

This work reports a theoretical study of the x-ray absorption near-edge structure spectra at the Cu K edge in several Cu(II) complexes with N -coordinating ligands showing a square-planar arrangement around metal cation. It is shown that single-channel multiple-scattering calculations are not able to reproduce the experimental spectra. The comparison between experimental data and ab initio computations indicates the need of including the contribution of two electronic configurations (3 d9 and 3 d10 L) to account for a proper description of the final state during the photoabsorption process. The best agreement between theory and experiment is obtained by considering a relative weight of 68% and 32% for the two absorption channels 3 d10 L and 3 d9, respectivelyComisión Interministerial de Ciencia y Tecnología MAT2002-04178-C04-03, BQU2002-02217 y BQU2002- 04364-C02-0

X-ray magnetic circular dichroism measurements using an X-ray phase retarder on the BM25 A-SpLine beamline at the ESRF

6 páginas, 8 figuras.Circularly polarized X-rays produced by a diamond X-ray phase retarder of thickness 0.5 mm in the Laue transmission configuration have been used for recording X-ray magnetic circular dichroism (XMCD) on the bending-magnet beamline BM25A (SpLine) at the ESRF. Field reversal and helicity reversal techniques have been used to carry out the measurements. The performance of the experimental set-up has been demonstrated by recording XMCD in the energy range from 7 to 11 keV.This work was partially supported by a Spanish CICYTMAT2008- 06542-C04 grant. MALM and RB acknowledge the Ministerio de Ciencia e Innovación of Spain for their Postdoctoral and PhD grants, respectively. We also acknowledge the Spanish Ministerio de Ciencia e Innovación and Consejo Superior de Investigaciones Científicas for financial support.Peer reviewe

New opportunities in trace elements structural characterization: high-energy X-ray absorption near-edge structure spectroscopy

Garnets in lower crustal mafic and ultramafic rocks usually contain rare-earth elements (REE) in trace concentrations. Direct characterization of REE at trace levels in natural garnets is not available in the literature because of the difficulty of obtaining structural information by means of conventional diffraction methods. Here, the characterization of Nd at trace levels (176-1029 p.p.m.) in a set of natural garnets performed by means of Nd K-edge X-ray absorption near-edge structure spectroscopy is presented, showing the capability of high-energy XANES for REE in trace structural determinations

Double-channel excitation in the XAS spectra of divalent and trivalent iron complexes in water solution.

We present a detailed analysis of XAS spectra of divalent and trivalent iron complexes in water solutions. The interpretation of the spectra has been provided by multi-channel multiple scattering approach. On this basis, good agreement between experimental data and theoretical calculations has been obtained in both cases including two excitation channels in the final state

X-ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X-ray absorption near-edge structure (XANES) spectroscopy study at the Ni K-edge in the early stages of growth of NiO on non-ordered SiO2, Al2O3 and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq-ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq-ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross-linking bonds Ni - O - M (M = Si, Al, Mg) at the interfaceThis work was partially supported by the Spanish CONSOLIDER Project FUNCOAT CSD2008-00023, the ENE2010-21198-C04-04 and MAT2011-27573-C04-04 projects and by the Aragón DGA NETOSHIMA grant. We acknowledge the Spanish Ministerio de Ciencia e Innovación and CSIC for financial support and for provision of synchrotron radiation and we would like to thank the staff of SpLine at ESRF and KMC2 at BESSY II for technical support. The research leading to these results has received funding from the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement No. 2267

Dynamics of AC susceptibility and coercivity behavior in nanocrystalline TbAl1.5 Fe0.5 alloys

The static and dynamic magnetic macroscopic properties of bulk and nanocrystalline TbAl1.5Fe0.5 alloys have been investigated. In bulk state, this alloy is understood as a reentrant ferromagnet. This is characterized by a ferromagnetic Curie transition at 114 K, as deduced from magnetization including Arrott plots, higher than that of TbAl2. The reentrance is found at lower temperatures, below 66 K, with a cluster glass behavior setting in, deduced from the magnetization irreversibility. This is accompanied by an abrupt increase in the coercivity from 0.08 kOe to 15 kOe at 5 K, with respect to the TbAl2 alloy. Room temperature Mössbauer spectroscopy confirms the paramagnetic state of such a bulk alloy. The spin dynamics within the disordered magnetic state is described by the AC-susceptibility which shows a Vogel–Fulcher law for the slowing down process. This is caused by a random anisotropy affecting the existing clusters. The production of milled TbAl1.5Fe0.5 alloys enhances the presence of magnetic disorder and results in the particle downsizing toward the nanocrystalline state (close to 10 nm). In this case, two frequency-dependent contributions exist, with different activation energies, one of them cannot be described by ideal spin glass nor blocking/unblocking (nanoparticle) processes. In addition, the coercivity reduces to 1 kOe with the decrease in the size as a consequence of the existence of single domain particles. The results are explained by the intricate interplay between exchange interactions and magnetocrystalline anisotropy with disorder and size effects. © 2012 Elsevier B.V.This work has been supported by the MAT2008-06542-C04 and MAT2011-27573-C04 projects.Peer Reviewe

X-ray magnetic circular dichroism measurements using an X-ray phase retarder on the BM25 A-SpLine beamline at the ESRF

The experimental set-up at SpLine (BM25A, ESRF) to measure XMCD by using a diamond X-ray phase retarder to obtain circularly polarized X-rays is described

Transport, electronic, and structural properties of nanocrystalline CuAlO2 delafossites

10 páginas, 10 figuras, 1 tabla.-- PACS number(s): 72.80.Jc, 71.38.Ht, 61.05.cj, 78.70.Dm.-- et al.This work reports on the effect of grain size on the electrical, thermal, and structural properties of CuAlO2 samples obtained by solid-state reaction combined with ball milling. Electrical characterization made in microcrystalline and nanocrystalline samples shows that the electrical conductivity decreases several orders of magnitude for the nanocrystalline samples, and, in addition, there is a large discrepancy between the activation energies associated to thermoelectric power ES. The study of the Cu K-edge x-ray absorption spectra of the CuAlO2 samples shows that the local structure around Cu is preserved after the sintering process, indicating that the observed behavior of the electrical conductivity is of intrinsic origin. Complex conductivity measurements as a function of frequency allow us to discard grain-boundaries effects on the electrical transport. Thus, the changes in σ(T) and S(T) are interpreted in terms of charge localization in the framework of small polarons. This is in agreement with the analysis of the near-edge region of the absorption spectra, which indicates that sintering favors the Cu-O hybridization. As a consequence, oxygen atoms progressively lose their capability of trapping holes, and the electrical conductivity is also enhanced.We acknowledge financial support by JCCM through Projects No. PAI-05-013 and PCI08-0091, and the Spanish CICYT through Grants No. MAT2008-06542-C04-01 and MAT2008-06517-C02. R.B. acknowledges support from the Ministerio de Ciencia e Innovación of Spain.Peer reviewe