Aneta Slodczyk

Probing the Nanodomain Origin and Phase Transition Mechanisms in (Un)Poled PMN-PT Single Crystals and Textured Ceramics

Outstanding electrical properties of solids are often due to the composition heterogeneity and/or the competition between two or more sublattices. This is true for superionic and superprotonic conductors and supraconductors, as well as for many ferroelectric materials. As in PLZT ferroelectric materials, the exceptional ferro- and piezoelectric properties of the PMN-PT ((1−x)PbMg1/3Nb2/3O3−xPbTiO3) solid solutions arise from the coexistence of different symmetries with long and short scales in the morphotropic phase boundary (MPB) region. This complex physical behavior requires the use of experimental techniques able to probe the local structure at the nanoregion scale. Since both Raman signature and thermal expansion behavior depend on the chemical bond anharmonicity, these techniques are very efficient to detect and then to analyze the subtitle structural modifications with an efficiency comparable to neutron scattering. Using the example of poled (field cooling or room temperature) and unpoled PMN-PT single crystal and textured ceramic, we show how the competition between the different sublattices with competing degrees of freedom, namely the Pb-Pb dominated by the Coulombian interactions and those built of covalent bonded entities (NbO6 and TiO6), determine the short range arrangement and the outstanding ferro- and piezoelectric properties.

Proton content and nature in perovskite ceramic membranes for medium temperature fuel cells and electrolysers.

Recent interest in environmentally friendly technology has promoted research on green house gas-free devices such as water steam electrolyzers, fuel cells and CO2/syngas converters. In such applications, proton conducting perovskite ceramics appear especially promising as electrolyte membranes. Prior to a successful industrial application, it is necessary to determine/understand their complex physical and chemical behavior, especially that related to proton incorporation mechanism, content and nature of bulk protonic species. Based on the results of quasi-elastic neutron scattering (QNS), thermogravimetric analysis (TGA), Raman and IR measurements we will show the complexity of the protonation process and the importance of differentiation between the protonic species adsorbed on a membrane surface and the bulk protons. The bulk proton content is very low, with a doping limit (~1–5 × 10−3 mole/mole), but sufficient to guarantee proton conduction below 600 °C. The bulk protons posses an ionic, covalent bond free nature and may occupy an interstitial site in the host perovskite structure.

Testing the Chemical/Structural Stability of Proton Conducting Perovskite Ceramic Membranes by in Situ/ex Situ Autoclave Raman Microscopy

Ceramics, which exhibit high proton conductivity at moderate temperatures, are studied as electrolyte membranes or electrode components of fuel cells, electrolysers or CO2 converters. In severe operating conditions (high gas pressure/high temperature), the chemical activity towards potentially reactive atmospheres (water, CO2, etc.) is enhanced. This can lead to mechanical, chemical, and structural instability of the membranes and premature efficiency loss. Since the lifetime duration of a device determines its economical interest, stability/aging tests are essential. Consequently, we have developed autoclaves equipped with a sapphire window, allowing in situ Raman study in the 25–620 °C temperature region under 1–50 bar of water vapor/gas pressure, both with and without the application of an electric field. Taking examples of four widely investigated perovskites (BaZr0.9Yb0.1O3−δ, SrZr0.9Yb0.1O3−δ, BaZr0.25In0.75O3−δ, BaCe0.5Zr0.3Y0.16Zn0.04O3−δ), we demonstrate the high potential of our unique set-up to discriminate between good/stable and instable electrolytes as well as the ability to detect and monitor in situ: (i) the sample surface reaction with surrounding atmospheres and the formation of crystalline or amorphous secondary phases (carbonates, hydroxides, hydrates, etc.); and (ii) the structural modifications as a function of operating conditions. The results of these studies allow us to compare quantitatively the chemical stability versus water (corrosion rate from ~150 µm/day to less than 0.25 µm/day under 200–500 °C/15–80 bar PH2O) and to go further in comprehension of the aging mechanism of the membrane.

Stress and temperature driven phase transitions in single crystalline KNbO 3 and textured KNL-NTS ceramics: A Raman andthermal expansion study

Lead-free KNbO<inf>3</inf> single crystals and ((K<inf>0.38</inf>Na<inf>0.52</inf>Li<inf>0.04</inf>)-(Nb<inf>0.86</inf>Ta<inf>0.1</inf>Sb<inf>0.04</inf>)O<inf>2.97</inf> textured ceramics were investigated as a function of temperature using Raman spectroscopy and loading dilatometry.

Stress-modified phase transitions in polarized PMN-PIN-PT, KN and KNL-NTS single crystals/textured ceramics: Thermal expansion and Raman scattering studies

Piezoelectric PMN-PIN-PT as well as lead-free KN and KNL-NST analogues in the form of single crystals or textured ceramics were investigated as a function of temperature and/or applied stress using Raman spectroscopy and dilatometry. The results reveal: 1) the 1st order character of the 120°C-transition in PMN-PIN-PT; 2) a previously unreported stress dependent phase transition in KN at 70°C; 3) important structural and dielectric changes in the case of KNL-NST ceramics in comparison with KN.