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Titanium silicon carbide (Ti3SiC2) powder was synthesized by molten salt shielded synthesis route of elemental reactants. Potassium bromide (KBr) was used for gas-tight encapsulation of the consolidated reaction mixture for further high temperature processing. The synthesis of Ti3SiC2 powder was carried out in air, the salt cladding and molten salt pool provided for the protection of the material against oxidation both at low and high temperature. The process yielded free flowing Ti3SiC2 powders without the need of a milling step. Al addition to the reaction mixture resulted in a high purity (96 wt. %) of Ti3SiC2 at a synthesis temperature of 1250 °C. The synthesized micro-metric Ti3SiC2 can be milled to nano-metric powders.

One of the necessary prerequisites to advance the electrochemical performance of Li7La3Zr2O12 (LLZ) based all-solid-state lithium batteries is the manufacturing of dense composite cathodes from cathode active material (CAM) and the LLZ ceramic solid electrolyte. However, free co-sintering of LLZ and CAM mixtures requires temperatures above 1000 °C which often leads to decomposition and secondary phase formation, especially for high energy CAMs. In our study we present a completely dry processing route which is fast, free of any sintering additives and coatings and suitable to fabricate dense mixed cathodes, pure LLZ separators and multilayers of the two. Through application of high mechanical pressure during Field-Assisted Sintering we were able to reduce the sintering temperature down to 675–750 °C with dwell times as low as 10 min, while still obtaining 95% theoretical density for LCO/LLZ mixtures. The low sintering temperature is suitable for high energy CAMs, but leads to a significant effect of surface impurities, especially from powder handling in air, and affects the crystallinity of the CAM/LLZ interface. In the present paper we investigate the impact of resulting interfaces on the ionic conductivity, the interfacial impedance and the cycling stability of produced cells and propose the optimization strategy.

In this work, silicon–hafnia (Si-HfO2, 80/20 mol. %) feedstock was plasma sprayed for Environmental Barrier Coating bond coat application. In the as-sprayed coating, hafnium disilicide (HfSi2), HfO2 tetragonal (t), and cubic (c) phases with a total volume of ~20 % were detected together with Si and HfO2 monoclinic (m). The temperature-dependent evolution of these phases was analyzed and paired with microstructural observations. It was found that above 700 °C, HfSi2 oxidizes and HfO2 (t) and (c) transforms into (m) polymorph. Up to this temperature, as-sprayed coating showed a non-linear expansion behavior. Estimated volume expansion at ~750 °C was 3.6 % based on dilatometry measurement. The primary and secondary mechanisms leading to the expansion in the coating were identified as oxidation of HfSi2 and polymorphic phase transitions in HfO2, respectively. As a consequence of the volume expansion, the coating was extensively cracked during cyclic oxidation and hence not protective anymore. After 100 h at 1300 °C, the volume fraction of oxidation product SiO2 was significant in the coating (0.34), while HfO2 was largely consumed (0.1) in the formation of HfSiO4 (0.56). This result suggested that reversible α↔β phase transitions in SiO2-cristobalite could be another factor contributing to the cracking in the coating during cyclic oxidation.

Journal of thermal spray technology : JTST (2020). doi:10.1007/s11666-020-01139-x, Published by Springer, Boston, Mass.

Dense protective layers are needed to reduce chromium-related degradation in SOFC stacks. In particular, atmospheric plasma sprayed (APS) Mn1.0Co1.9Fe0.1O4 (MCF) coatings demonstrated low degradation rates in stack tests. We show that short-term annealing in air induces crack healing within these coatings. Parallel to this effect, a phase transformation is observed originating from oxidation that proceeds by solid state-diffusion. The present contribution reveals the basic mechanisms of the microstructural and phase changes of coatings in long-term annealing tests of up to 10,000 h at 700 °C. The layer develops differently at the air-facing surface and in the bulk. Due to cation deficiency, oxidation is dominated by cation outward diffusion, leading to a Co-enriched surface layer. The bulk displays a fine distribution of the initial (rock salt) and the final (spinel) phases. Understanding the mechanisms leading to these irreversible changes enables predictions to be made concerning durable protectivecoatings in SOFCs.

The thermal stability of LiCoMnO4 and LiCoMnO4 with 1 wt.-% LiF as an additive was compared upon heating in air. The stoichiometries of samples heat-treated at 700, 800, 900 and 1000 °C were analyzed by means of inductively coupled plasma optical emission spectroscopy for cation contents, inert gas fusion analysis for oxygen, and nuclear reaction analysis for fluorine contents, revealing that the sample chemistries remain constant except for oxygen. The oxygen content of the samples correlates with the Li2MnO3 secondary phase fraction, which forms upon heating, as is shown by X-ray powder diffraction. For each temperature, a greater amount of Li2MnO3 is formed in the samples with LiF addition than in the single LiCoMnO4 samples. In situ high-temperature X-ray powder diffraction between 650 and 950 °C demonstrates that LiCoMnO4 with LiF addition exhibits the same kind of decomposition reactions upon heating and cooling as the sample without LiF addition. However, for the samples with LiF addition, the formation of the decomposition product, Li2MnO3, is accelerated due to the excess Li through LiF addition, i.e. the stability of the spinel phase decreases due to the supply of lithium. Since lithium is consumed by Li2MnO3 formation and fluorine remains in the samples, we can also conclude that the fluorine anion is incorporated into the spinel or Li2MnO3 phase upon heating LiCoMnO4 and LiF together.

The formation and decomposition of aluminum titanate (Al2TiO5, tialite) in feedstock powders and coatings of the binary Al2O3-TiO2 system are so far poorly understood. A commercial fused and crushed Al2O3-40%TiO2 powder was selected as the feedstock for the experimental series presented in this paper, as the composition is close to that of Al2TiO5. Part of that powder was heat-treated in air at 1150 and 1500 °C in order to modify the phase composition, while not influencing the particle size distribution and processability. The powders were analyzed by thermal analysis, XRD and FESEM including EDS of metallographically prepared cross sections. Only a maximum content of about 45 wt.% Al2TiO5 was possible to obtain with the heat treatment at 1500 °C due to inhomogeneous distribution of Al and Ti in the original powder. Coatings were prepared by plasma spraying using a TriplexPro-210 (Oerlikon Metco) with Ar-H2 and Ar-He plasma gas mixtures at plasma power levels of 41 and 48 kW. Coatings were studied by XRD, SEM including EDS linescans of metallographically prepared cross sections, and microhardness HV1. With the exception of the powder heat-treated at 1500 °C an Al2TiO5-Ti3O5 (tialite–anosovite) solid solution Al2−xTi1+xO5 instead of Al2TiO5 existed in the initial powder and the coatings.

With the aim of improving the electrochemical properties of the LiCoMnO4 high-voltage spinel for lithium ion battery applications, LiCoMnO4-yFy (y = 0, 0.05, 0.1) compounds were synthesized by a two-step solid-state reaction at 800 °C. The stoichiometry of the samples was verified by nuclear reaction analysis for the fluorine stoichiometry, inert gas fusion analysis for the oxygen stoichiometry, and inductively coupled plasma optical emission spectroscopy for the cation stoichiometry. X-ray diffraction analysis and scanning electron microscopy revealed increasing phase purity and changing microstructure upon fluorine incorporation. Electrochemical characterizations were carried out in battery test cells using a liquid electrolyte. The samples show poor coulombic efficiency, due to liquid electrolyte decomposition. However, fluorinated spinels demonstrated significantly improved capacities of up to 18% and improved cycling stability of up to 20%, compared to their non-fluorinated counterparts.

Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe3O5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this study, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe3O5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mossbauer spectrometry, and scanning electron microscopy. Results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.

Chromium evaporation barriers are frequently used in solid oxide fuel cells to protect the porous cathode from chromium poisoning. Volatile chromium species are generated at the operation temperature of about 600–900 °C in a humid atmosphere for chromia scale forming steels as interconnect materials. In order to reduce this effect, barrier coatings are applied, often by atmospheric plasma spraying. However, also in these coatings microstructural changes as densification and in parallel formation of large pores have been observed. In order to clarify these mechanisms plasma sprayed Mn1.0 Co1.9Fe0.1O4 (“MCF”) are deposited on ferritic steels and furthermore coated with a perovskite based contact layer as used in stack build-up. These coatings are annealed in air up to 1000 h and the microstructural changes and bending of the samples are studied. The results show increasing bending with increasing aging time. High temperature curvature measurements indicate that the amount of bending is not significantly dependent on temperature. As an explanation the creep deformation of the substrate/coating system at high temperatures due to compressive stress levels in the coating is given. The origin of the stress is related to phase changes in combination with the oxidation of the coatings. In addition, interdiffusion and densification processes are discussed.

Atmospheric plasma sprayed (APS) Al2O3 TiO2 coatings have found a wide range of industrial application due to their favorable properties in combination with low costs and a high availability. However, the detailed effect of the phase composition and the element distribution of the feedstock powders on the coating properties and the spraying process has only crudely been investigated so far. Here the impact of aluminum titanate (Al2TiO5) on the microstructural features and mechanical properties of Al2O3 40 wt.% TiO2 APS coatings is demonstrated by investigating the detailed phase composition and the distribution of aluminum and titanium in three different fused and crushed feedstock powders and the respective coatings. Thereby, a direct influence of the Al2TiO5 on the deposition efficiency, the porosity, the elastic modulus, and the hardness of the coatings is revealed. In particular, the feedstock powder had a stronger effect on the coating properties than increasing the stand off distance from 150 to 350 mm. Furthermore, Al2TiO5 coatings were found to exhibit a strong texture. The obtained results emphasize the need for a more detailed specification of commercial Al2O3 TiO2 feedstock powders in terms of their phase composition and elemental homogeneity to ensure a high reliability of the coating process and ultimately the coating properties.

This work presents a systematic study of the lanthanum tungstate (LaWO) ceramic layers formation on porous metallic substrates as a function of the PS-PVD processing parameters including plasma characteristics, support type and temperature, as well as addition of O2 during the spraying. Through precise control of the PS-PVD parameters, a set of processing conditions were found that led to He gas-tight purely cubic LaWO layers with negligible secondary phase precipitations. Being dependent on process conditioning, the formation and evolution of the cubic La6−xWO12−δ (x = 0.3-0.6) as the main phase of functional importance and of the undesired secondary phases (La2O3 and La6W2O15) was strongly affected by the cation and oxygen stoichiometries. The rapid cooling of the feedstock at particle impact on the substrate led to the formation of highly La-saturated compositions which exhibited significant lattice expansion in comparison with conventionally processed LaWO and is considered beneficial in terms of material performance. And indeed, the H2 permeation performance of the PS-PVD processed LaWO ceramic layers shown earlier by our group was 0.4 ml/min∙cm2 at 825 °C for 60 µm thickness of the functional layer, the highest value reported for this type of proton conducting ceramics, so far.

The purpose of this research was to investigate the corrosion behavior of the low/high Yb2SiO5 containing Yb2Si2O7 coatings under high-velocity water vapor flow. To that end, Yb2Si2O7 and Si coatings were deposited by atmospheric plasma spraying on SiC substrates. The corrosion tests were performed in the burned natural gas under atmospheric pressure, with a gas flow velocity of 100 m/s at 1200 °C for 200 h. After the test, a 25 mm thick, porous corrosion layer at the surface of the Yb2Si2O7 rich coatings was found accompanied with a mass reduction, whereas samples with Yb2SiO5 rich coatings showed mass gain indicating the greater resistance of Yb2SiO5 against water vapor. A comparison of the Yb2Si2O7 rich coatings tested in this work and Yb2Si2O7 bulk samples tested in an earlier work at the same facility revealed significantly different recession rates. Possible mechanisms responsible for this distinct behavior are discussed in the manuscript.

La0.58Sr0.4Co0.2Fe0.8O3− δ (LSCF) deposited on a metallic porous support by plasma spray-physical vapor deposition is a promising candidate for oxygen-permeation membranes. Ionic transport properties are regarded to depend on the fraction of perovskite phase present in the membrane. However, during processing, the LSCF powder decomposes into perovskite and secondary phases. In order to improve the ionic transport properties of the membranes, spraying was carried out at different oxygen partial pressures p(O2). It was found that coatings deposited at lower and higher oxygen partial pressures consist of 70% cubic/26% rhombohedral and 61% cubic/35% rhombohedral perovskite phases, respectively. During annealing, the formation of non-perovskite phases is driven by oxygen non-stoichiometry. The amount of oxygen added during spraying can be used to increase the perovskite phase fraction and suppress the formation of non-perovskite phases.

The hydrogen bond in K3H(SO4)2 was investigated using a neutron single crystal diffraction technique at room temperature and 2.3 K. The title compound crystallizes in the monoclinc space group A12/...

Dense coatings on metallic interconnectors are necessary to suppress chromium poisoning of SOFC cathodes. Atmospherically plasma sprayed (APS) Mn1.0Co1.9Fe0.1O4 (MCF) protective layers demonstrated reduced chromium related degradation in laboratory and stack tests. Previous analyses revealed strong microstructural changes comparing the coating's as-sprayed and operated condition. This work concentrates on the layer-densification and crack-healing observed by annealing APS-MCF in air, which simulates the cathode operation conditions. The effect is described by a volume expansion induced by a phase transformation. Reducing conditions during the spray process lead to a deposition of the MCF in a metastable rock salt configuration. Annealing in air activates diffusion processes for a phase transformation to the low temperature stable spinel phase (T < 1050 °C). This transformation is connected to an oxygen incorporation which occurs at regions facing high oxygen partial pressures, as there are the sample surface, cracks and pore surfaces. Calculations reveal a volume expansion induced by the oxygen uptake which seals the cracks and densifies the coating. The process decelerates when the cracks are closed, as the gas route is blocked and further oxidation continues over solid state diffusion. The self-healing abilities of metastable APS coatings could be interesting for other applications.

[EN] Hydrogen permeation membranes are a key element in improving the energy conversion efficiency and decreasing the greenhouse gas emissions from energy generation. The scientific community faces the challenge of identifying and optimizing stable and effective ceramic materials for H-2 separation membranes at elevated temperature (400-800 degrees C) for industrial separations and intensified catalytic reactors. As such, composite materials with nominal composition BaCe0.8Eu0.2O3-delta:Ce0.8Y0.2O2-delta revealed unprecedented H-2 permeation levels of 0.4 to 0.61 mL center dot min(-1)center dot cm(-2) at 700 degrees C measured on 500 mu m-thick-specimen. A detailed structural and phase study revealed single phase perovskite and fluorite starting materials synthesized via the conventional ceramic route. Strong tendency of Eu to migrate from the perovskite to the fluorite phase was observed at sintering temperature, leading to significant Eu depletion of the proton conducing BaCe0.8Eu0.2O3-delta phase. Composite microstructure was examined prior and after a variety of functional tests, including electrical conductivity, H-2-permeation and stability in CO2 containing atmospheres at elevated temperatures, revealing stable material without morphological and structural changes, with segregation-free interfaces and no further diffusive effects between the constituting phases. In this context, dual phase material based on BaCe0.8Eu0.2O3-delta:Ce0.8Y0.2O2-delta represents a very promising candidate for H-2 separating membrane in energy-and environmentally-related applications, This work has been conducted with the financial support by the Helmholtz Association under the Research Programme Energy Efficiency, Materials and Resources. Financial funding from the Spanish Government (ENE2014-57651 and SEV-2012-0267 grants) is also gratefully acknowledged. ZEA-3 at FZJ is gratefully acknowledged for performing the ICP-OES analysis.

[EN] La0.58Sr0.4Co0.2Fe0.8O3-delta (LSCF), deposited on a metallic porous support by plasma spray -physical vapor deposition (PS-PVD) is a promising candidate for oxygen -permeation membranes. However, after O-2 permeation tests, membranes show vertical cracks leading to leakage during the tests. In the present work, one important feature leading to crack formation was identified. More specifically; membrane residual stress changes during thermal loading were found to be related to a phase transformation in the support. In order to improve the performance of the membranes, the metallic support was optimized by applying an appropriate heat treatment. The observed oxygen fluxes during permeation tests had infinite selectivity and were amongst the highest fluxes ever measured for LSCF membranes in the thickness range of 30 mu m, supported by LSCF porous substrates. (C) 2016 Elsevier B.V. All rights reserved., The authors gratefully acknowledge Mr. Ralf Laufs for his help with the use of the PS-PVD facility, the preparation of the SEM and EDS investigations by Dr. Doris Sebold and Mr. P. Terberger for calculations and discussion of Thermocalc phase diagrams (Forschungszentrum Julich, IEK-1). The work on membranes by PS-PVD was part of the DEMOYS Project funded from the European Community's Seventh Framework Program, FP7/2007-2013, under grant agreement No. 241309.

The highly disordered crystal structure of triammonium hydrogen disulfate, (NH4)3H(SO4)2, in the high-temperature phase I was studied using single-crystal neutron diffraction. It is known that the O atom involved in hydrogen bonding between neighbouring SO4 tetrahedra is disordered and takes a split-atom position, building a two-dimensional hydrogen-bond network in the (001) plane. The H atoms in these SO4–H—SO4 hydrogen bonds are disordered and hence refined with a split-atom model. Moreover, from the much larger anisotropic mean-square displacements of ammonium protons the NH_4^+ groups were refined with a reasonable split-atom model, and their motional behaviour was also analysed by rigid-body treatment. Finally, careful consideration was given to show possible supplementary proton migration between the ammonium protons and those of the hydrogen bonds in this high-temperature phase.

X-ray powder diffraction, differential scanning calorimetry (DSC)/thermogravimetry (TG) and single-crystal neutron diffraction methods were used to investigate triammonium hydrogen disulfate (NH4)3H(SO4)2 (TAHS) in the temperature range between 293 and 493 K. The temperature-dependent X-ray powder diffraction measurements show a clear hysteresis of the I \leftrightarrow II phase transition of TAHS with transition temperatures of T up = 412.9 (1) K on heating and of T down = 402.6 (1) K on cooling. From the existence of hysteresis and from the jump-like changes of the lattice parameters, the I \leftrightarrow II phase transition of TAHS is considered to be first order. With DSC/TG measurements we confirmed that there is only one phase transition between 293 and 493 K. Through careful investigation on single crystals of TAHS using neutron diffraction, the correct space group (C2/c) of room-temperature TAHS-II phase was confirmed. Crystal structure analysis by single-crystal neutron diffraction showed a strongly elongated displacement ellipsoid of the proton which lies in the middle of the (SO4)H(SO4) dimer with \bar 1 local symmetry. The protons of the NH4 groups also show strongly enlarged anisotropic mean-square displacements. These findings are interpreted in terms of a characteristic proton disorder in the TAHS-II phase.

Perovskitic oxides are widely investigated as oxygen transport membrane materials for the efficient generation of pure oxygen or the use in membrane reactors. However, most of high performance perovskites suffer from low stability in operation conditions. Therefore, solid solutions of SrTi1−xFexO3−δ (STF) are investigated due to the initial high stability of the strontium titanate host lattice. Self-synthesized powders with substitution of Ti by 0%, 25%, 35%, 50%, 75%, and 100% Fe were studied. Crystal structure, functional properties i.e., diffusion coefficient, surface exchange rates, and oxygen permeation rates as well as membrane fabrication and operation related material properties i.e. sintering behaviour and thermal/chemical expansion were investigated. Substitution of Ti by Fe increases oxygen mobility and, hence, oxygen permeation rates, but reduces stability in operation relevant atmospheres such as Ar/4%H2 or CO2. At the same time thermal/chemical expansion increases. This makes the fabrication of supported thin membranes and their integration into membrane modules more challenging. It turned out that 25–35% Fe substituting Ti seems to be a good compromise between structural and functional properties. Oxygen permeation rates achieved are comparable to that of standard materials such as La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF). At the same time stability is higher and thermal expansion coefficients lower compared to LSCF, which makes STF with limited Fe-content (max. 35%) a promising oxygen transport membrane material.