Analysis of corrosion layers on protective coatings and high temperature materials in simulated service environments of modern power plants using SNMS, SIMS, SEM, TEM, RBS and X-ray diffraction studies.

In three different examples, the effects of the oxidation behaviour as well as the microstructural stability of high temperature materials and protective coatings was determined by combining the results of kinetic studies with extensive analytical investigations using, among other techniques, SNMS, SIMS, SEM, TEM, Rutherford back scattering (RBS) as well as X-ray diffraction. 1). The effect of water vapour on the oxidation behaviour of 9% Cr steels in simulated combustion gases has been determined. The effects of O2 and H2O content on the oxidation behaviour of 9% Cr steel in the temperature range 600-800 degrees C showed that in dry oxygen a protective scale was formed with an oxidation rate controlled by diffusion in the protective scale. In the presence of water vapour, after an incubation period, the scales became non-protective as a result of a change in the oxidation limiting process. The destruction of the protective scale by water vapour does not only depend on H2O content but also on the H2O/O2-ratio. 2). The increase of component surface temperature in modern gas turbines leads to an enhanced oxidation attack of the blade coating. Improvements in corrosion resistance and longer lifetime thermal barrier coatings in gas turbines have been achieved by improvement of the high temperature properties of MCrAlY coatings by additions of minor alloying elements such as yttrium, silicon and titanium. 3). The use of oxide dispersion strengthened (ODS) alloys provides excellent creep resistance up to much higher temperatures than can be achieved with conventional wrought or cast alloys in combination with suitable high temperature oxidation/corrosion resistance. Investigation of the growth mechanisms of protective chromia and alumina scales were examined by a two-stage oxidation method with 18O tracer. The distribution of the oxygen isotopes in the oxide scale was determined by SIMS and SNMS. The results show the positive influence of a Y2O3 dispersion on the oxidation resistance of the ODS alloys and its effect on growth mechanisms.

Internal transitions of negatively charged magnetoexcitons and many body effects in a two-dimensional electron gas.

Internal transitions of quasi-two-dimensional, negatively charged magnetoexcitons ( X-) and their evolution with excess electron density have been studied in GaAs/AlGaAs quantum wells. In the dilute electron limit, due to magnetic translational invariance, the optically detected resonance spectra are dominated by bound-to-continuum bands in contrast to the negatively charged donor system D-, which exhibits strictly bound-to-bound transitions. With increasing excess electron density Landau-level filling factors nu<2 the X--like transitions are blueshifted; they are absent for nu>2. The blueshifted transitions are explained in terms of a new type of collective excitation---magnetoplasmons bound to a mobile valence band hole.

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

Analysis of chemical interactions between stabilized zirconia and perovskites.

LaMnO(3)-based perovskites are used as cathode materials in solid oxide fuel cells (SOFC). A major aspect for their applicability is their chemical inertness in connection with the electrolyte material YSZ (Zr(0.85)Y(0.15)O(1.93)) against zirconate formations. Perovskites with the composition La(y-x)(Sr, Ca)(x)Mn(1-u)Co(u)O(3) (y = 1.0 and 0.95; x = 0- 0.2 and 1; u = 0 and 0.2) were investigated with regard to their reactivity with YSZ at different reaction times and temperatures. Powder mixtures and double-layer reaction couples were used for the investigations. XRD phase analyses, SEM/EDX and EPMA were applied for the characterization of the annealed samples. La-deficient perovskites (y = 0.95) partially substituted by Sr and Ca improve the chemical compatibility of perovskite compositions towards YSZ. Sr-containing perovskites were found to have a higher reactivity than Ca perovskites for La(2)Zr(2)O(7) formation. On the other hand enhanced Ca diffusion into YSZ was observed. Co substitution on Mn lattice sites decreased the chemical compatibility, especially for Sr containing perovskites.

TEM and SNMS studies of protective alumina scales on NiCrAlY-alloys.

The effect of Si addition on the oxidation behaviour of NiCrAlY alloys in the temperature range 950 bis 1100 degrees C has been investigated. During isothermal oxidation oxide growth rates were practically independent of the Si-content. However during cyclic oxidation Si additions were beneficial. Si additions of 1-2(m)/(0) appeared to shift the onset for spallation to longer times. It was found that Si stabilizes the beta-phase and probably it suppresses the formation of metastable Al(2)O(3) modifications.

Stress measurement in alumina scales on high temperature alloys using X-ray stress evaluation and laser Raman spectroscopy.

The effect of silicon and titanium on the spallation resistance of alumina scales grown on NiCrAlY-type alloys has been investigated using model alloys with different additions of Si or Ti. For this purpose cyclic oxidation experiments have been carried out at temperatures between 950 and 1100 degrees C. After various times stresses in selected Si-doped samples have been determined by X-ray stress evaluation (XSE) at ambient temperature. The compressive stresses in the scales have been found to increase with an increasing oxidation time tending to become constant for long times. The development of stress is affected by the presence of Si. Laser Raman spectroscopy (LRS) has been calibrated for strain measurement using XSE results. Then LRS has been applied for strain measurement at higher temperatures.

Optical emission spectroscopy in reactive hollow cathode arc discharge plasmas - Local distribution of active species during the deposition of hard carbon films.

A low pressure arc plasma discharge from a hollow LaB(6)-cathode with up to 100 A discharge current is used to create plasmas of high density. Typical values for the electron density and temperature in PETRA ( Plasma Engineering and Technology Research Assembly) are n(e)=10(12)-10(13) cm(-3) and T(e)=5-20 eV. The ionization ratio is typically 1-10%. Optical emission spectroscopy has been applied to investigate the processes within the plasma which lead to the deposition of thin carbon films. In these experiments hydrogenated carbon films (a-C:H) have been deposited on Si-substrates by introducing hydrocarbon gases (CH(4), C(2)H(2)) into He- and Ar-plasmas. Space resolved optical emission spectroscopy using an in-situ translation mechanism of the optical fibre has been performed to measure the local concentrations of CH-radicals, carbon ions and of the excitation of He-neutrals. In addition the hydrogen liberated by the dissociation of the hydrocarbon molecules has been measured. The dissociation of the hydrocarbon molecules takes place as a localized process in the vicinity of the reactive gas inlet.

Local optical emission spectroscopy of excited species effused from an evaporation cell and a sputter source into dense plasmas - Basic studies for the deposition of thin gradient films.

Space resolved optical emission spectroscopy has been applied to determine the distribution of excited species in dense plasmas which are used for the deposition of thin coatings. Typical electron densities and electron temperatures in the plasma facility PETRA ( Plasma Engineering and Technology Research Assembly) are in the range of n(e) = 10(12) cm(-3) and T(e) = 10 eV. During the deposition process material (Al) is evaporated from a vapour cell under controlled conditions. The vapour stream is guided into a dense plasma which is composed of inert gas, Ar or He, and hydrocarbon species produced from the dissociation of C(2)H(2). The evaporated Al-stream which travels with thermal velocity into a plasma of high electron density, is nearly completely ionized due to the short mean free path for electron impact ionization in the above mentioned parameter range. Optical emission spectroscopy has been applied to investigate the interaction processes between the vapour stream and the plasma as well as the transport of the ionized Al along the applied magnetic field. For the measurements space resolved optical emission spectroscopy with an in-situ translation mechanism of the optical fibre has been used to measure the local concentrations of excited Al neutrals and ions as well as the concentration of the background plasma species.

Determination of lattice and grain boundary diffusion coefficients in protective alumina scales on high temperature alloys using SEM, TEM and SIMS.

Grain and grain boundary diffusion coefficients in alumina scales on FeCrAl-based ODS alloys have been determined. The boundary diffusion-coefficients have been derived by combining gravimetrically determined growth rate data with SEM and TEM analyses of the oxide scale microstructure. The diffusion coefficients determined have been used as input parameters for a computer model describing the oxygen isotope exchange between grain and grain boundary in the alumina scale which forms during a two-stage oxidation using (18)O-tracers. This comparison of the calculated tracer profiles with profiles determined experimentally by SIMS allows the estimation of the lattice diffusion coefficient of oxygen in the alumina scale.