In this study, cathode performance of cost-effective inert substrate-supported solid oxide fuel cells fabricated by a single step cosintering process is investigated. The polarization resistance of cosintered inert substrate-supported cathode symmetrical cells (ISC) is compared with the polarization resistance of electrolyte-supported symmetrical cells (ESC) prepared by post- and cosintering. ESC prepared by cosintering have similar polarization resistance than ESC prepared by post-firing due to the addition of pore formers. However, the implementation of a porous inert substrate increases the polarization resistance. Analysis of electrochemical impedance spectra could exclude a gas-phase diffusion limitation due to the porous substrate. Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) reveals an accumulation of zinc, magnesium and silicon on the inner pore surface of the cathode layer. Thermodynamic calculations confirm desorption of these elements from the silicate substrate during the cosintering. In addition, a zinc manganite spinel is detected in the cathode layer via confocal Raman spectroscopy, which indicates a reaction between the cathode material and zinc. The larger cathode polarization resistance of the inert substrate-supported cell is attributed to microstructural changes and the coverage of the cathode surface.

In the present work, the influence of deuterium on the microstructure of a duplex stainless steel type EN 1.4462 has been characterized by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) supported by scanning electron microscopy (SEM), focused ion beam (FIB), electron back scattered diffraction (EBSD) and energy dispersive x-ray (EDX) investigations. Characterization has been carried out before and after electrochemical charging with deuterium which has been used as a tracer, due to its similar behavior to hydrogen in the steel microstructure. In a first approach, the distribution of the deuterium occurring at temperatures above −58°C has been visualized. Further it turned out that sub-surface micro blisters are formed in the ferrite-austenite interface, followed by the formation of needle shaped plates and subsequent cracking at the ferrite surface. In the austenite phase, parallel cracking alongside twins and hexagonal close packed (martensitic) regions has been observed. In both phases and even in the apparent interface, cracking has been associated with high deuterium concentrations, as compared to the surrounding undamaged microstructure. Sub-surface blistering in the ferrite has to be attributed to the accumulation and recombination of deuterium at the ferrite-austenite interface underneath the respective ferrite grains and after fast diffusing through this phase. Generally, the present application of chemometric imaging and structural analyses allows characterization of hydrogen assisted degradation at a sub-micron lateral resolution.

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and high‐resolution scanning electron microscopy are well‐acknowledged tools in materials characterization. The ability to map chemical species on the surface of an investigated sample with often low mass detection limits makes ToF‐SIMS an essential tool in fields where many question marks concerning degradation processes and damage mechanisms exist. The aim of this paper is to describe the power of data fusion of ToF‐SIMS and high‐resolution scanning electron microscopy results employing computational methods for multivariate data analysis such as principal component analysis. As a case study the investigation of hydrogen distribution in an artificially charged duplex stainless steel microstructure is presented aiming on a better understanding of hydrogen embrittlement. Copyright © 2016 John Wiley & Sons, Ltd.

Oxygen ion conduction in Nd3+‐doped Pb(ZrxTi1−x)O3 (PZT) was investigated by impedance spectroscopy and 18O‐tracer diffusion with subsequent secondary ion mass spectrometry (SIMS) analysis. Ion blocking electrodes lead to a second relaxation feature in impedance spectra at temperatures above 600°C. This allowed analysis of ionic and electronic partial conductivities. Between 600°C and 700°C those are in the same order of magnitude (10−5–10−4 S/cm) though very differently activated (2.4 eV vs. 1.2 eV for ions and electron holes, respectively). Oxygen tracer experiments showed that ion transport mainly takes place along grain boundaries with partly very high local ionic conductivities. Numerical analysis of the tracer profiles, including a near‐surface space charge zone, revealed bulk and grain‐boundary diffusion coefficients. Calculation of an effective ionic conductivity from these diffusion coefficients showed good agreement with conductivity values determined from impedance measurements. Based on these data oxygen vacancy concentrations in grain boundary and bulk could be estimated. Annealing at high temperatures caused a decrease in the grain‐boundary ionic conductivity and onset of additional defect chemical processes near the surface, most probably due to cation diffusion.

In this study, the contribution of grain boundaries to the oxygen reduction and diffusion kinetics of La0.8Sr0.2MnO3 (LSM) thin films is investigated. Polycrystalline LSM thin films with columnar grains of different grain sizes as well as epitaxial thin films were prepared by pulsed laser deposition. (18)O tracer exchange experiments were performed at temperatures from 570 °C to 810 °C and subsequently analyzed by secondary ion mass spectrometry (SIMS). The isotope concentration depth profiles of polycrystalline films clearly indicate contributions from diffusion and surface exchange in grains as well as in grain boundaries. Measured depth profiles were analyzed by finite element modeling and revealed the diffusion coefficients D and oxygen exchange coefficients k of both the grain bulk and grain boundaries. Values obtained for grain boundaries (Dgb and kgb) are almost three orders of magnitude higher than those of the grains (Dg and kg). Hence, grain boundaries may not only facilitate fast oxygen diffusion but also fast oxygen exchange kinetics. Variation of the A-site stoichiometry ((La0.8Sr0.2)0.95MnO3) did not lead to large changes of the kinetic parameters. Properties found for epitaxial layers without grain boundaries (Db and kb) are close to those of the grains in polycrystalline layers.

A novel operation mode for time of flight-secondary ion mass spectrometry (ToF-SIMS) is described for a TOF.SIMS 5 instrument with a Bi-ion gun. It features sub 100 nm lateral resolution, adjustable primary ion currents and the possibility to measure with high lateral resolution as well as high mass resolution. The adjustment and performance of the novel operation mode are described and compared to established ToF-SIMS operation modes. Several examples of application featuring novel scientific results show the capabilities of the operation mode in terms of lateral resolution, accuracy of isotope analysis of oxygen, and combination of high lateral and mass resolution. The relationship between high lateral resolution and operation of SIMS in static mode is discussed. (C) 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Oxygen isotope exchange experiments are performed in donor doped PbZrxTi1 − xO3 (PZT) under field load. A detailed mapping of the oxygen tracer ions and thus indirectly of the oxygen vacancy distribution is enabled by spatially resolved time-of-flight secondary ion mass spectrometry (ToF-SIMS). Hence, knowledge can be gained on the oxygen vacancy redistribution under the influence of high electric fields applied to Cu inner electrodes of a PZT multilayer stack. Upon field load an enhanced oxygen tracer concentration is measured near to the cathode and interpreted in terms of a field-driven oxygen vacancy accumulation at an oxide ion blocking Cu cathode. Oxygen tracer depth profiles in near-anode and near-cathode diffusion zones give quantitative information on local grain and grain boundary diffusion coefficients and their dependence on applied voltages.

The considerable potential of model-type thin film electrodes for the investigation of oxygen exchange pathways is demonstrated for different electrode materials on yttria-stabilized zirconia (YSZ). In particular, a correlation of voltage-driven 18O tracer experiments and electrical ac and dc measurements has proven to be helpful when aiming at mechanistic conclusions. For Pt electrodes, two different parallel reaction pathways can be identified under equilibrium conditions. At lower temperatures, a diffusion limited path through the electrode is dominant, whereas at higher temperatures, an electrode surface path with oxygen incorporation at the three-phase boundary determines the electrochemical activity. In addition, for high cathodic polarization, an electrolyte surface path with electron transfer via YSZ outperforms both other pathways. The oxygen incorporation zones of the bulk path as well as the electrolyte surface path can be visualized by 18O tracer incorporation experiments in combination with time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis. A successful separation of surface and bulk path can also be obtained for La0.8Sr0.2MnO3−δ (LSM) electrodes by means of 18O tracer incorporation at different cathodic overpotentials. Under lower polarization, a surface path with oxygen incorporation at the three-phase boundary is dominant, whereas at higher cathodic overpotential, the bulk path becomes significantly more pronounced. These changes are discussed in terms of polarization-induced changes of the ionic conductivity in the LSM electrode. Measurements on the acceptor-doped perovskite-type materials La0.6Sr0.4CoO3−δ (LSC) and La0.6Sr0.4FeO3−δ (LSF) illustrate the limitations of the tracer incorporation method. In the case of highly active LSC electrodes with low polarization resistances, the tracer distribution is determined by the electrolyte, and thus the active sites of the electrodes can no longer be visualized. The effect of polarization-induced changes of the electrode’s electronic conductivity is demonstrated for LSF. Only a region close to the current collector remains electrochemically active owing to limited lateral electron transport.

Oxygen isotope exchange with subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a highly valuable tool for determining oxygen diffusion coefficients in oxides. Since ToF-SIMS analysis enables an elemental and chemical mapping, it can also be used to visualize oxygen exchange-active zones by determining the local oxygen isotopic fraction. However, measuring accurate isotopic fractions can be a challenging analytical task owing to secondary ion interaction and signal saturation, particularly when dealing with high secondary ion intensities as commonly found when analyzing oxygen ions from oxides. It is shown that in many cases the calculated O-18(-) fraction erroneously shifts to higher values and can lead to systematic errors in the determination of diffusion coefficients. A novel ToF-SIMS operation mode, called "Collimated Burst Alignment" (CBA) mode, is therefore introduced to enable a more accurate determination of oxygen isotopic fractions with an optimized lateral resolution of sub-100 nm. Both improvements are rendered possible by a modified beam guidance in the primary ion gun. This modification reduces detector dead time effects and ion interactions to a minimum and secondary ion intensities can be obtained more accurately. The result of this optimization is demonstrated in measurements of the natural isotope abundance of several different oxides including SrTiO3 and Sr-doped LaCoO3.

Bioresorbable materials for implants have become increasingly researched over the last years. The bone-implant-interfaces of three different implant materials, namely a new bioresorbable magnesium alloy, a new self-reinforced polymer implant and a conventional titanium alloy, were tested using various methods: push-out tests, SEM and EDX analyses as well as surface analyses based on stereoscopic 3D pictures were conducted. The fracture energy is proposed as a very significant reference value for characterizing the mechanical performance of a bone-implant system. By using a video-extensometer system instead of, as is commonly done, tracking the movement of the crosshead in the push-out tests, the accuracy of measurement could be increased.