Elaboration and TEM structural study of interfaces in composites produced by precipitation

Model ceramic matrix composites have been manufactured in a wide range of materials using the precipitation of a metal (Cu, Ni, Cr) in a ceramic matrix (nitride AIN or oxides MgO, Al2O3) providing, in each case low energy configurations at the heterophase interfaces. In connection to microelectronic applications, copper metallic particles precipitate in AIN after implantation by copper ions and anneal of the ceramic matrix. Faceted particles are imaged by HRTEM and are associated to a low energy structural and chemical configuration. Internal reduction experiments have been carried out on (Mg,Ni)O, (Mg,Cu)O and (Al,Cr)2O3 mixed oxides; the morphology, chemical composition and orientation relationship of the different precipitates are obtained through TEM observations and discussed in terms of interfacial energy and precipitate growth mechanism and kinetics. Conventional and high resolution TEM in conjonction to structural models have allowed a comprehensive description of the interface

Impedance of SOFC electrodes: A review and a comprehensive case study on the impedance of LSM:YSZ cathodes

AbstractIt was shown through a comprehensive impedance spectroscopy study that the impedance of the classic composite LSM:YSZ (lanthanum strontium manganite and yttria stabilized zirconia) solid oxide fuel cell (SOFC) cathode can be described well with porous electrode theory. Furthermore, it was illustrated through a literature review on SOFC electrodes that porous electrode theory not only describes the classic LSM:YSZ SOFC cathode well, but SOFC electrodes in general. The extensive impedance spectroscopy study of LSM:YSZ cathodes consisted of measurements on cathodes with three different sintering temperatures and hence different microstructures and varying degrees of LSM/YSZ solid state interactions. LSM based composite cathodes, where YSZ was replaced with CGO was also studied in order to acquire further knowledge on the chemical compatibility between LSM and YSZ. All impedance measurements were acquired in the very broad temperature range of 200–900°C for complete elucidation of the impedance. All impedance spectra were analyzed in terms of porous electrode theory. Physical materials parameters were extracted from the analysis, which were in excellent accordance with literature values. Valuable insight about the dissolution of Mn in the cathode composite material YSZ during preparation was furthermore provided along with valuable engineering characteristics such as the electrochemical utilization thickness. From the combined impedance study and literature review, it is clear, that porous electrode theory is the most suitable framework for any type of porous composite SOFC electrode evaluation

La and Sm Co-doped SrTiO3-delta Thermoelectric Ceramics

The thermoelectric properties of Sr1-xLax/2Smx/2TiO3-δ (0.05 ≤ x ≤ 0.30) ceramics have been investigated with compositions batched, synthesised by solid state reaction and sintered in 5% H2/N2 at 1500 °C for 6 hrs. All X-ray diffraction patterns were fully indexed according to a cubic perovskite phase. Scanning electron microscopy revealed homogeneous grain structure in the ceramics and confirmed relative density ≥ 89%. The electrical conductivity (σ) of x ≤ 0.15 displayed metallic behaviour with σ < 1000 S/cm, whereas x ≥ 0.20 were semiconducting with σ < 250 S/cm. The Seebeck coefficient of all compositions was negative indicating n-type behaviour. Within this series, x = 0.20 displayed the lowest thermal conductivity of ∼ 3 W/m.K (at 973 K), x = 0.10 displayed the highest power factor of 1400 μW/K2.m (at 573 K) and overall x = 0.15 had the highest dimensionless figure of merit (ZT) of 0.24 (at 875 K)

Reversible Decomposition of Secondary Phases in BaO Infiltrated LSM Electrodes-Polarization Effects

In operando Raman spectroscopy is used to study ceramic La0.85Sr0.15MnO3 +/-delta electrodes infiltrated with BaO. The aim of this work is to clarify why BaO infiltration reduces the polarization resistance in oxygen containing atmospheres. Prior to the in operando experiments, ex situ X-ray diffraction and Raman spectroscopy reveal the formation of a secondary phase, Ba3Mn2O8, on the electrode. During the in operando Raman investigation of the BaO-infiltrated La0.85Sr0.15MnO3 +/-delta electrodes, experiments are performed at 300 and 500 degrees C with oxygen partial pressure 0.1 atm and with -1 or +1 V applied potential. A changing electrode surface is observed during operation as the Ba3Mn2O8 secondary phase decomposes and manganese oxide accumulates on the electrode surface during cathodic polarization. The observed changes are reversible. These results suggest that the formation of Ba3Mn2O8 is responsible for the reduced polarization resistance observed at open circuit voltage (OCV) in an oxygen containing atmosphere. Furthermore, the results illustrate the dramatic differences between the electrode surface composition at OCV and during cathodic polarization. Overall, the results highlight the dynamic interactions between minor secondary phases and applied potential, a general effect that may be important for the high-performance frequently observed with ceramic electrodes prepared by infiltration

Chromium deposition and poisoning of La0.8Sr0.2MnO3 oxygen electrodes of solid oxide electrolysis cells

The effect of the presence of an Fe–Cr alloy metallic interconnect on the performance and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes is studied for the first time under solid oxide electrolysis cell (SOEC) operating conditions at 800 °C. The presence of the Fe–Cr interconnect accelerates the degradation and delamination processes of the LSM oxygen electrodes. The disintegration of LSM particles and the formation of nanoparticles at the electrode/electrolyte interface are much faster as compared to that in the absence of the interconnect. Cr deposition occurs in the bulk of the LSM oxygen electrode with a high intensity on the YSZ electrolyte surface and on the LSM electrode inner surface close to the electrode/electrolyte interface. SIMS, GI-XRD, EDS and XPS analyses clearly identify the deposition and formation of chromium oxides and strontium chromate on both the electrolyte surface and electrode inner surface. The anodic polarization promotes the surface segregation of SrO and depresses the generation of manganese species such as Mn2+. This is evidently supported by the observation of the deposition of SrCrO4, rather than (Cr,Mn)3O4 spinels as in the case under the operating conditions of solid oxide fuel cells. The present results demonstrate that the Cr deposition is essentially a chemical process, initiated by the nucleation and grain growth reaction between the gaseous Cr species and segregated SrO on LSM oxygen electrodes under SOEC operating conditions

Tuning the thermoelectric properties of A-site deficient SrTiO3 ceramics by vacancies and carrier concentration

Ceramics based on Sr0.8La0.067Ti0.8Nb0.2O3-δ have been prepared by the mixed oxide route. The La1/3NbO3 component generates ∼13.4% A-site vacancies; this was fixed for all samples. Powders were sintered under air and reducing conditions at 1450 to 1700 K; products were of high density (>90% theoretical). Processing under reducing conditions led to the formation of a Ti1-xNbxO2-y second phase, core-shell structures and oxygen deficiency. X-ray diffraction (XRD) confirmed a simple cubic structure with space group Pm3[combining macron]m. Transmission electron microscopy revealed a high density of dislocations while analytical scanning transmission electron microscopy at atomic resolution demonstrated a uniform distribution of La, Nb and vacancies in the lattice. X-ray photoemission spectroscopy and thermogravimetry showed the oxygen deficiency (δ value) to be ∼0.08 in reduced samples with enhanced carrier concentrations ∼2 × 1021 cm-3. Both carrier concentration and carrier mobility increased with sintering time, giving a maximum figure of merit (ZT) of 0.25. Selective additional doping by La or Nb, with no additional A site vacancies, led to the creation of additional carriers and reduced electrical resistivity. Together these led to enhanced ZT values of 0.345 at 1000 K. The contributions from oxygen vacancies and charge carriers have been investigated independently

Enhancing the thermoelectric power factor of Sr0.9Nd0.1TiO3 through control of the nanostructure and microstructure

Donor-doped SrTiO3 ceramics are very promising n-type oxide thermoelectrics. We show that significant improvements in the thermoelectric power factor can be achieved by control of the nanostructure and microstructure. Using additions of B2O3 and ZrO2, high density, high quality Sr0.9Nd0.1TiO3 ceramics were synthesised by the mixed oxide route; samples were heat treated in a single step under reducing atmosphere at 1673 K. Synchrotron and electron diffraction studies revealed an I4/mcm tetragonal symmetry for all specimens. Microstructure development depended on the ZrO2 content; low level additions of ZrO2 (up to 0.3 wt%) led to a uniform grain size with transformation-induced sub-grain boundaries. HRTEM studies showed a high density of dislocations within the grains; the dislocations comprised (100) and (110) edge dislocations with Burger vectors of d(100) and d(110) respectively. Zr doping promoted atomic level homogenization and a uniform distribution of Nd and Sr in the lattice, inducing greatly enhanced carrier mobility. Transport property measurements showed a significant increase in the power factor, mainly resulting from the enhanced electrical conductivity while the Seebeck coefficients were unchanged. In optimised samples a power factor of 2.0 × 10−3 W m−1 K−2 was obtained at 500 K. This is an ∼30% improvement compared to the highest values reported for SrTiO3-based ceramics. The highest ZT value for Sr0.9Nd0.1TiO3 was 0.37 at 1015 K. This paper demonstrates the critical importance of controlling the structure at the atomic level and the effectiveness of minor dopants in enhancing the thermoelectric response