Interface stability between bare, Mn-Co spinel coated AISI 441 stainless steel and a diopside-based glass-ceramic sealant

This document is the Accepted Manuscript version of the following article: A. G. Sabato, A. Crysanthou, M. Salvo, G. Tempura, and F. Smeacetto, ‘Interface stability between bare, Mn-Co spinel coated AISA 441 stainless steel and a diopside-based glass-ceramic sealant’, International Journal of Hydrogen Energy, Vol. 43 (13): 1824-1834, January 2018, made available under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License CC BY NC-ND 4.0 ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited, and is not altered, transformed, or built upon in any way. Under embargo until 16 December 2018. The final, definitive version of this paper is available online at doi: https://doi.org/10.1016/j.ijhydene.2017.11.150.This study is focused on a diopside-based glass-ceramic sealant for solid oxide fuel cells and its compatibility with AISI 441 stainless steel interconnect. The morphological and chemical stability with both bare and Mn–Co spinel coated AISI 441 steel, after 3500 h exposure at 800 °C in air, is reviewed and discussed. Post-mortem samples are morphologically and chemically analysed by SEM-EDS. Reaction products at the glass-ceramic/bare AISI 441 interface, resulting from the reaction of Mg from the sealant and Cr and Mn from the steel, are detected, without affecting negatively the integrity of the joints. In the case of Mn–Co spinel coated AISI 441, interactions between the glass-ceramic and the outer part of the Mn–Co spinel coating, along with crystallization of oxides rich in Si and Mg, are detected, but still no corrosion phenomena are present. The glass-ceramic is found to be compatible with both bare and coated AISI 441.Peer reviewe

Electrophoretic co-deposition of Mn1.5Co1.5O4, Fe2O3 and CuO: Unravelling the effect of simultaneous addition of Cu and Fe on the microstructural, thermo-mechanical and corrosion properties of in-situ modified spinel coatings for solid oxide cell interconnects

A systematic microstructural, thermo-mechanical and electrical characterization of simultaneous Fe–Cu doped Mn–Co spinel coatings processed by electrophoretic co-deposition on Crofer 22 APU is here reported and discussed. An innovative approach for the simultaneous electrophoretic deposition of three spinel precursors is designed, conceived and optimised, with the aim of outlining time- and energy-saving spinel modification routes. The effect of different levels of Cu and Fe co-doping is observed on the stability of the modified Mn–Co spinel phase, the coefficient of thermal expansion (CTE), the corrosion resistance and on the densification behaviour of the obtained coatings. Cu determines an increase of CTE, while Fe has the opposite behavior. The synergic effect of the simultaneous Fe and Cu co-doping results in an improved densification and the stabilization of the MnCo2O4 cubic phase. The most interesting results in terms of corrosion resistance are obtained for the Mn1.28Co1.28Fe0.15Cu0.29O4 spinel

Recent advances on spinel-based protective coatings for solid oxide cell metallic interconnects produced by electrophoretic deposition

The application of ceramic protective coatings to the metallic interconnects in solid oxide cells (SOCs) is a viable and effective method to limit interconnect degradation issues. This featured letter provides a critical overview of the main outcomes of current research on the use of the electrophoretic deposition (EPD) technique to produce protective coatings for SOC metallic interconnects, specifically focusing on different approaches to stabilise spinel-based suspensions, as well as the possible sintering procedures. The protective properties of EPD coatings are reviewed and discussed in terms of oxidation kinetics and area specific resistance evaluation

Electrophoretic Deposition of Ceramic Coatings for Solid Oxide Cells: Challenges and Perspectives

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Optimization of electrophoretic deposition technique to control doping and densification of protective spinel coatings for SOC interconnects

Manganese cobaltite spinel coatings have been reported to limit oxidation and Cr-evaporation from ferritic stainless steel interconnects in solid oxide cell stacks; however, the implementation of the functional properties of the base Mn–Co spinel coating and compatibility with the substrate can be pursued through the optimisation of the coating composition, as well as the deposition method and sintering profile. Electrophoretic deposition (EPD) allows to deposit homogeneous layers in few seconds on complexly shaped steel components; it also offers the possibility to produce in-situ doped coatings, avoiding time and energy consuming multi-step processes. In this work, various EPD suspensions are optimised to achieve a single step co-deposition of CuO, Fe2O3 and Mn1,5Co1,5O4 on Crofer 22 APU. Different Fe-Cu doped Mn–Co spinel are successfully obtained by controlling the precursors amount in the EPD suspension and subsequent reactive sintering, as proved by detailed SEM and TEM analyses. Improved functional properties of produced coatings are evaluated in terms of oxidation kinetics and area specific resistance. Both the iron and copper amount in the coating and the sintering process significantly influence the coating densification, with benefits to the protective properties and thermomechanical compatibility with the interconnect

Mn-Co spinel coatings on Crofer 22 APU by electrophoretic deposition: Up scaling, performance in SOFC stack at 850 °C and compositional modifications

Ceramic coatings for metallic interconnects play a key role in limiting corrosion and chromium evaporation in solid oxide cells. This study presents the upscaling of the electrophoretic deposition (EPD) technique to process Mn-Co spinels on real-dimension Crofer 22 APU interconnects and the test in a SOFC stack. Area specific resistance of long-term test conducted for 5000 h at 850 °C demonstrated that two-steps sintering has a significant influence on the coating performance; an area specific resistance degradation rate of 0.5 mΩ cm2 kh−1 is recorded. Stack test, operated in fuel cell mode at 850 °C for 3000 h under application of 227 mA/cm², including 5 thermal cycles, demonstrated the effectiveness of the electrophoretically deposited Mn-Co spinel in limiting the oxide scale growth on the Crofer 22 APU. An advanced post mortem investigation showed the effectiveness of the EPD ceramic coating, even when considering different and complex surfaces of the Crofer 22 APU

Periodic nanostructures induced by point defects in Pb1-xSnxTe

Lead tin telluride solid solutions are excellent candidates for the p-type conduction legs of the thermoelectric generator modules. The investigation of their microstructure properties is an important issue, that can effectively modify their electronic and thermal transport properties. In this work, we show the experimental dependences of the Pb1-xSnxTe component distribution, which were identified as periodic nanostructures with an amplitude of λ ≈ 50-500 nm. The observed periodicity is explained by the generation and recombination of point defects due to diffusion processes during the synthesis, sintering, and annealing of samples. A model describing the formation of such inhomogeneities in Pb1-xSnxTe ternary alloys during isothermal annealing is proposed

Glass-ceramic sealant for solid oxide fuel cells application: Characterization and performance in dual atmosphere

This document is the Accepted Manuscript version of the following article: A. G. Sabato, G. Tempura, D. Montinaro, A. Chysanthou, M. Salvo, E. Bernardo, M. Secco, F. Meacetto, ‘Glass-ceramic sealant for solid oxide fuel cells application: characterization and performance in dual atmosphere’, Journal of Power Sources, Vol. 328:262-270, October 2016, doi: http://dx.doi.org/10.1016/j.jpowsour.2016.08.010. Published by Elsevier. This manuscript version is distributed distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License CC BY NC-ND 4.0 (http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited, and is not altered, transformed, or built upon in any way.Glass-ceramic composition was designed and tested for use as a sealant in solid oxide fuel cell (SOFC) planar stack design. The crystallization behaviour was investigated by calculating the Avrami parameter (n) and the activation energy for crystallization (Ec) was obtained. The calculated values for n and Ec were 3 and 413.5 kJ/mol respectively. The results of thermal analyses indicate that this composition shows no overlap between the sintering and crystallization stages and thus an almost pore-free sealant can be deposited and sintered at 850 °C in air for 30 min. A gas tightness test has been carried out at 800 °C for 1100 h in dual atmosphere (Ar-H2 and air) without recording any leakage. Morphological and crystalline phase analyses were conducted prior and following tests in dual atmospheres in order to assess the compatibility of the proposed sealant with the metallic interconnect.Peer reviewe

STEM-EDX and FIB-SEM Tomography of ALLVAC 718Plus Superalloy

Allvac 718Plus (718Plus) is a high strength, corrosion resistant nickel- based superalloy used for application in power generation, aeronautics and aerospace industry. The 718Plus microstructure consists of a γ matrix with γ’-Ni3(Al,Ti) and some δ- Ni3Nb phases as well as lamellar particles (η-Ni3Ti, η*-Ni6AlNb or Ni6(Al,Ti)Nb) precipitated at the grain boundaries. The primary strengthening mechanism for this alloy is a precipitation hardening, therefore size and distribution of precipitates are critical for the performance of the alloy. The aim of this study was to characterize precipitates in the 718Plus superalloy using Scanning Transmission Electron Microscope combined with Energy Dispersive X-ray Spectroscopy (STEM-EDX) and Focused Ion Beam Scanning Electron Microscope (FIB-SEM). The STEM-EDX and FIB-SEM tomography techniques were used for 3D imaging and metrology of the precipitates. Transmission electron microscopy and EDX spectroscopy were used to reveal details of the 718Plus microstructure and allow determine chemical composition of the phases. The study showed that electron tomography techniques permit to obtain complementary information about microstructural features (precipitates size, shape and their 3D distribution) in the reconstructed volume with comparison to conventional particle analysis methods, e.g. quantitative TEM and SEM metallography