Synthesis and Characterization of Fluorite-Type La2Ce2O7 Plasma Sprayable Powder for TBCs Application.

This work focuses on the fabrication of lanthanum cerate (La2Ce2O7, LC) powders via two chemical routes: modified Pechini sol-gel method and solid-state synthesis. The synthesized LC powders were heat treated in the temperature range of 1000-1400 °C for 6 h and investigated as a material for thermal barrier coating (TBC) applications. For this purpose, the powder morphology, chemical composition, crystal structure and thermal stability were studied. Scanning electron microscopy (SEM) of the synthesized powders revealed an agglomerated structure consisting of fine and uniformly distributed grains. Energy-dispersive X-ray spectroscopy (EDXS) indicated that the chemical compositions of the LC powders were similar to the stoichiometric ratio of La2Ce2O7. A cubic fluorite structure was observed by X-ray diffraction analysis (XRD) after calcining the LC powder prepared by solid-state synthesis at 1300 °C. In contrast, there was always a fluorite structure in the LC powder synthesized by the Pechini sol-gel method after heat treatment over the entire temperature range. The thermal behavior of the LC powders was analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) in the temperature range of 25-1300 °C. Neither an obvious mass change nor a visible energy change was observed within the tested temperature range, indicating high phase stability of the LC powder and its suitability for TBC applications. Spheroidization on the prepared LC powders was also investigated, revealing that powder size and morphology had a significant impact on the spheroidization efficiency.

Phase Evaluation, Mechanical Properties and Thermal Behavior of Hot-Pressed LC-YSZ Composites for TBC Applications.

In this work, La2Ce2O7-yttria-stabilized zirconia (LC-YSZ) composites with different weight fractions of YSZ (40−70 wt.%) were prepared by hot pressing at 1400 °C and investigated as a material for thermal barrier-coating (TBC) applications. For this purpose, the effect of YSZ addition on the phase composition, microstructure, mechanical performance and thermal behavior was studied. X-ray diffraction analysis showed that the LC-YSZ composites were mainly composed of a cubic ZrO2 and La2O3-CeO2-ZrO2 solid solution with a pyrochlore structure, indicating that the reaction between LC and YSZ took place during hot pressing. Scanning electron microscopy revealed the high microstructural stability of the prepared composites, as the pore formation was significantly controlled and a high relative density (>97%) was obtained. The microstructure of LC-YSZ bulk samples was relatively fine-grained, with an average grain size below or very close to 1 µm. YSZ doping improved the Vickers hardness of the LC-YSZ composites; the highest hardness, with value of 12 ± 0.62 GPa, was achieved for the composite containing 70 wt.% of YSZ. The fracture toughness of LC-YSZ composites was in the range from 2.13 to 2.5 MPa·m1/2. No statistically significant difference in heat capacity or thermal conductivity was found between the composites with different content of YSZ. The results showed that LC-YSZ composites have relatively low thermal conductivities from room temperature (1.5−1.8 W·m−1·K−1) up to 1000 °C (2.5−3.0 W·m−1·K−1). This indicates that the prepared LC-YSZ composite materials are promising candidates for TBC applications.

Hydrothermal Corrosion of Double Layer Glass/Ceramic Coatings Obtained from Preceramic Polymers.

Polysilazane-based double layer composite coatings consisting of a polymer-derived ceramic (PDC) bond-coat and a PDC top-coat that contains ceramic passive and glass fillers were developed. To investigate the environmental protection ability of the prepared coatings, quasi-dynamic corrosion tests under hydrothermal conditions were conducted at 200 °C for 48-192 h. The tested PDC coatings exhibited significant mass loss of up to 2.25 mg/cm2 after 192 h of corrosion tests, which was attributed to the leaching of elements from the PDC coatings to the corrosion medium. Analysis of corrosion solutions by inductively coupled plasma optical emission spectrometry (ICP-OES) confirmed the presence of Ba, Al, Si, Y, Zr, and Cr, the main component of the steel substrate, in the corrosion medium. Scanning electron microscopy (SEM) of the corroded surfaces revealed randomly distributed globular crystallites approximately 3.5 µm in diameter. Energy-dispersive X-ray spectroscopy (EDXS) of the precipitates showed the presence of Ba, Al, Si, and O. The predominant phases detected after corrosion tests by X-ray powder diffraction analysis (XRD) were monoclinic and cubic ZrO2, originating from the used passive fillers. In addition, the crystalline phase of BaAl2Si2O8 was also identified, which is in accordance with the results of EDXS analysis of the precipitates formed on the coating surface.

High-Temperature Oxidation Resistance of PDC Coatings in Synthetic Air and Water Vapor Atmospheres.

This work is aimed at the development and investigation of the oxidation behavior of ferritic stainless-steel grade AISI 441 and polymer-derived ceramic (PDC) protective coatings. Double-layer coatings of a PDC bond coat below a PDC top coat with glass and ceramic passive fillers' oxidative resistance were studied at temperatures up to 1000 °C in a flow-through atmosphere of synthetic air and in air saturated with water vapor. Investigation of the oxide products formed at the surface of the samples in synthetic air and water vapor atmospheres, at different temperatures (900, 950, 1000 °C) and exposure times (24, 96 h) was carried out on both uncoated steel and steel coated with selected coatings by scanning electron microscopy (SEM) and X-Ray diffraction (XRD). The Fe, Cr2O3, TiO2, and spinel (Mn,Cr)3O4 phases were identified by XRD on oxidized steel substrates in both atmospheres. In the cases of the coated samples, m- ZrO2, c- ZrO2, YAG, and crystalline phases (Ba(AlSiO4)2-hexacelsian, celsian) were identified. Scratch tests performed on both coating compositions revealed strong adhesion after pyrolysis as well as after oxidation tests in both atmospheres. After testing in the water vapor atmosphere, Cr ions diffused through the bond coat, but no delamination of the coatings was observed.

Y2O3-Al2O3 microsphere crystallization analyzed by electron backscatter diffraction (EBSD).

The crystallization of glass microspheres in the Y2O3-Al2O3-system produced from precursor powders of four different nominal compositions via flame synthesis is analyzed in detail by electron microscopy with a focus on electron backscatter diffraction (EBSD). Growth models are formulated for individual microspheres crystallized during flame synthesis as well as after an additional heat treatment step. 16 different types of crystallized bodies are cataloged for future reference. They are presented without regard for their relative occurrence; some are extremely rare but illustrate the possibilities of flame synthesis in the analyzed system. All three phases in the binary Y2O3-Al2O3-phase diagram (Y3Al5O12, YAlO3 and Y4Al2O9) and α-alumina are located by EBSD. Energy dispersive X-ray spectrometry results obtained from these microspheres show that their chemical composition can deviate from the nominal composition of the precursor powder. The multitude of differing microsphere types showing polygon and dendritic crystal growth as well as phase separation indicate that flame synthesis can lead to a wide variety of parameters during microsphere production, e.g. via irregular flight paths through the flame, contaminants or irregular cooling rates.

PDC Glass/Ceramic Coatings Applied to Differently Pretreated AISI441 Stainless Steel Substrates.

In this work, the influence of different cleaning procedures on adhesion of composite coatings containing passive ceramic and commercial glasses was investigated. Two compositions (C2c, D2-PP) of double-layer polymer-derived ceramic (PDC) coating systems, composed from bond coat and a top coat, were developed. In order to obtain adherent coatings, stainless steel substrates were cleaned by four different cleaning procedures. The coatings were then deposited onto the steel substrate via spray coating. Pretreatment by subsequent ultrasonic cleaning in acetone, ethanol and deionised water (procedure U) was found to be the most effective, and the resultant C2c and D2-PP coatings, pyrolysed at 850 °C, indicated strong adhesion without delamination or cracks, propagating at the interface steel/bond coat. In the substrate treated by sandblasting and chemical etching, small cracks in the bond coat were observed under the same pyrolysis conditions. After oxidation tests, all coatings, except for those subjected to the U-treated substrates, showed significant cracking in the bond coat. The D2-PP coatings were denser than C2c, indicating better protection of the substrate.