Tanja Damjanović

Synthesis and characterization of strontium titanate nanoparticles as potential high temperature oxygen sensor material

We present a simple and highly reproductive method for the preparation of thin films consisting of strontium titanate nanoparticles. The films are produced by spin coating of a sol on silicon targets and subsequent annealing under ambient conditions. Analysis by atomic force microscopy shows particles with typical sizes between 10nm and 50 nm. X-ray photoelectron spectroscopy displays a stoichiometry of the films as anticipated from preliminary experiments with strontium titanate single crystals. Metastable-induced electron spectroscopy and ultraviolet photoelectron spectroscopy are used as tools to give evidence to the similar electronic properties of nanoparticle film and single crystal. These results support the prospect for an application of the nanoparticle films as high temperature oxygen sensor with superior properties.

Preparation of SOFC Cells by Means of Electrophoretic Deposition

Solid oxide fuel cells with an electrode supported thin film electrolyte are a promising alternative to electrolyte supported single cells because of decreased electrolyte resistance. The electrophoretic deposition (EPD) of the electrolyte was performed on A-site deficient La0.75Sr0.2MnO3-δ (ULSM) from three different suspensions: (Y2O3)0.08(ZrO2)0.92 (YSZ), (Ce0.9Gd0.1)O1.955 (GDC) and La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) in acetylacetone and isopropanol. The thickness of the deposits was controlled by varying the conditions of the electrophoretic deposition. Because of porosity reduction in the cathode layer during sintering of the electrolytes we deposited porous cathodes (La0.8Sr0.2MnO3-δ (LSM) and La0.6Sr0.4Fe0.8Co0.2O3-δ (LSCF) ) as well as anodes (NiO/YSZ and NiO/GDC) on dense YSZ foils by applying a conductive layer on top of the surface part to be coated.

Modelling and Experimental Verification of the Oxidation Protection of C/C-Si-SiC Composites with Mullite

The protectiveness of mullite layers electrophoretically deposited on C/C-Si-SiC composites, against isothermal oxidation in air in the temperature range from 1200 to 1550 °C, was investigated by means of thermogravimetry (TG). The experimental results are interpreted with the help of a phenomenological model. At lower temperatures or short oxidation times the overall oxidation kinetics is determined by transport processes in the EPD mullite layer, which leads to a linear growth law. At higher temperatures or longer times of oxidation the oxidation rate is controlled by solid-state diffusion processes in the growing silica layer, which leads to a parabolic growth law. Comparison of experimental parabolic and linear rate constants with calculated ones suggests, in the framework of the model, the conclusion that carbon monoxide (CO) diffusion in the oxide layers is the rate determining step for the overall oxidation of the C/C-Si-SiC substrates.

Synthesis and Electrophoretic Deposition of an Yttrium Silicate Coating System for Oxidation Protection of C/C-Si-SiC Composites

Due to favorable chemical and mechanical properties of yttrium silicate coatings (low Young’s modulus, low thermal expansion coefficient, low evaporation rate and oxygen permeability, good erosion resistance), this material is a promising complement to SiC coatings for protecting C/C-Si-SiC composites. For the preparation of silicate powders, the Pechini method was used. As a coating method, electrophoretic deposition from stable suspensions based on isopropanol was chosen. Under controlled deposition voltage and duration, coatings of various thicknesses were deposited. The deposited layers were characterized by SEM and EDX analysis. The protectiveness of these coatings was tested by isothermal thermogravimetry.

Electrophoretic Deposition of Thin SOFC-Electrolyte Films on Porous La0,75Sr0,2MnO3-δ Cathodes

Solid oxide fuel cells with an electrode supported thin film electrolyte (electrolyte thickness 5 μm < d < 20 μm) are a promising alternative to electrolyte supported single cells because of decreased electrolyte resistance. The electrophoretic deposition (EPD) was performed on A-site deficient La0.75Sr0.2MnO3(ULSM) from three different suspensions: (Y2O3)0.08(ZrO2)0.92 (YSZ), (Ce0.9Gd0.1)O1.955 (GDC) and La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) in acetylacetone and isopropanol. The thickness of the deposits was controlled by varying the conditions of the electrophoretic deposition.

Electrophoretic Deposition of Mullite Based Oxygen Diffusion Systems on C/C-Si-SiC Composites

Combining sol-gel synthesis of 3/2 mullite through hydrolysis and condensation of tetraethoxysilane and aluminum-tri-sec-butylate with electrophoretic deposition (EPD) yields sufficiently thick and homogeneous layers which transform into mullite at T ≥ 1000 °C. The characterisation of the mullite precursor during synthesis was performed through electroacustic measurements. The protectiveness of the deposited mullite layers was tested in air in the temperature range 1200 °C ≤ T ≤ 1550 °C by means of isothermal thermogravimetric analysis for up to 200 hours. Comparing the oxidation rate of mullite coated C/C-Si-SiC samples to that of uncoated reference samples clearly demonstrated that mullite offers a significant improvement to the oxidation resistance of the uncoated material. At temperatures above 1600 °C the protectiveness of the deposited layer is reduced due to the existence of a liquid phase and the formation of CO bubbles above the cracks in the SiC layer. In order to prolong the protectiveness of our mullite layers at higher temperatures we deposited an additional layer from a suspension of mullite precursor with 5 wt. % of Al2O3 powder. The protectiveness of so obtained mullite and mullite/ Al2O3 layers was also tested under cyclic conditions at 1500 °C and 1550 °C. These experiments clearly demonstrated that all samples withstood at least for 4-10 cycles which were performed subsequently in different time intervals (from 2-3 days to 1 h).

Modeling of Electrophoretic Deposition of Oxides on C/C-SiC-Composites

Electrophoretic deposition is a versatile coating technique for poorly conducting materials on sufficiently well conducting substrates, e.g. oxides are deposited on highly conductive carbon composites covered by a moderately conductive SiC layer. A numerical simulation based on the solution of the Laplace equation is applied to different geometries. The calculations yield potential distributions and current densities, which are directly connected with the oxide mass deposited on the samples. The calculated results are compared with the experimentally obtained values and satisfactory agreement is found. Further, the model reproduces the main features of the currentvoltage relation.

Galvanostatic Electrophoretic Deposition of Yttriumsilicate on C/C-Si-SiC Composites

The use of carbon fibre reinforced carbon composites in oxidizing atmospheres is limited to temperatures below 400 °C. To benefit from their excellent mechanical strength that is still preserved at high temperatures, suitable oxidation protection coating systems have to be developed. Composites which are capillary infiltrated with Si and coated with SiC via chemical vapour deposition show significantly enhanced oxidation resistance. For the increase of service temperature above 1300 °C, high temperature stable materials with low oxygen diffusivities such as yttrium silicates have to complement the SiC coating. The electrophoretic deposition performed under constant current conditions leads to relatively high green densities and therefore good sinterability of the applied coatings. In this work we present the preparation of suspensions, their characterization regarding particle size and electrophoretic mobility for yttrium silicate powder prepared by the solid state method. Depending on particle charge and conductivity of the investigated suspensions iodine is employed to increase particle charge. The use of current densities between 0.5-5mA/cm² leads to smooth and homogeneous layers. Layers sintered as low as 1400 °C for 2h already show promising protection of the C/C-Si-SiC substrate during thermogravimetric analysis.

Synthesis and Electrophoretic Deposition of Mullite Precursor Sols for the Oxidation Protection of Carbon Fibre Reinforced Composites

The preparation of mullite coatings for the oxidation protection of carbon fibre reinforced composites using a combination of sol-gel synthesis and electrophoretic deposition (EPD) has been investigated. Mullite precursor sols were synthesised by controlled hydrolysis and condensation reactions of the metal alkoxides TEOS (tetraethoxysilane) and Al(OBus)3 (aluminiumtri-sec-butylate). The structure and properties of the mullite precursor were strongly influenced by the synthesis parameters, especially by the water to TEOS ratio (rw/Si) and the pH value of the water. A variety of synthesis conditions was tested for optimising the mullite precursor sols regarding their suitability for the electrophoretic deposition. The electrokinetic behaviour of the sols and the charging of the sol particles which is necessary for a successful EPD were investigated by measurements of the Electrokinetic Sonic Amplitude (ESA signal). 29Si CP/MAS NMR measurements were used to get information about the coordination of the silicon and the homogeneity of the Al/Si distribution in the precursors. Heat-treated samples were characterised by X-ray diffraction for investigating the mullite formation. Coatings prepared by EPD and sintering at 1300 °C in Ar enabled an effective oxidation protection in the temperature range 1200 °C ≤ T ≤ 1550 °C.