Glass/steel/clay interactions in a simulated radioactive waste geological disposal system.

Deep geological storage is the accepted solution for the final disposal of high-level radioactive waste therefore, it is necessary to study the host rock of the planned Hungarian waste repository and the materials involved in the engineered barriers. The main goal was to understand the characteristics and stability of the glass/steel/claystone system, from the structural properties of the vitrified waste (borosilicate glasses) to the clay response in the repository. Repository conditions were applied during the experiments to understand the chemical evolution of the system. A triplicate setup was kept at 80 °C for 3, 7 and 12 months and post-mortem characterization was performed. No alteration products were observed with scanning electron microscopy energy dispersive X-ray spectroscopy measurements on the surface of the glass and Fe or in the clay after the end of the experimental period. Based on the elemental analysis of the liquid phase, the released amount of B, K, Si and Na increased, while that of Ca and Mg decreased compared to the baseline. The concentrations of Cl- and SO42- did not change significantly. Ca- and Mg-silicate precipitation was observed by X-ray photoelectron spectroscopy at the surface range of the borosilicate glasses because of the synthetic porewater treatment.

Energy loss function of samarium.

We present a combined experimental and theoretical work to obtain the energy loss function (ELF) or the excitation spectrum of samarium in the energy loss range between 3 and 200 eV. At low loss energies, the plasmon excitation is clearly identified and the surface and bulk contributions are distinguished. For the precise analysis the frequency-dependent energy loss function and the related optical constants (n and k) of samarium were extracted from the measured reflection electron energy loss spectroscopy (REELS) spectra by the reverse Monte Carlo method. The ps- and f-sum rules with final ELF fulfils the nominal values with 0.2% and 2.5% accuracy, respectively. It was found that a bulk mode locates at 14.2 eV with the peak width ~6 eV and the corresponding broaden surface plasmon mode locates at energies of 5-11 eV.

In-situ formation of Ag nanoparticles in the MAO coating during the processing of cp-Ti.

Silver nanoparticle (Ag-NP) containing antibacterial micro-arc oxidation (MAO) coatings have already been synthesized over titanium-based materials via the MAO process employed in silver acetate (AgC2H3O2) containing electrolyte. However, the way of incorporation and in-situ formation of Ag-NPs within the MAO coating have not been documented yet. Present work was initiated to reveal the mechanism of Ag-NP formation within the MAO coatings. Thus, the structure of the MAO coating fabricated on commercial purity titanium in the AgC2H3O2-containing electrolyte was investigated by electron microscopy techniques. To this end, the cross-sectional high-resolution electron microscopy studies were carried out on lamella cut out with the focused ion beam technique, and these investigations were backed by X-ray photoelectron spectroscopy measurements of chemical composition on the surface of the MAO coating. These studies revealed that Ag is dispersed in the form of nanoparticles throughout the coating and that a higher density was confirmed closer to the micro-pores.

Optical properties of amorphous carbon determined by reflection electron energy loss spectroscopy spectra.

We present the combined experimental and theoretical investigations of the optical properties of amorphous carbon. The reflection electron energy loss spectra (REELS) spectra of carbon were measured using a cylindrical mirror analyzer under ultrahigh vacuum conditions at primary electron energies of 750, 1000 and 1300 eV. The energy loss function and thereby the refractive index n and the extinction coefficient k were determined from these REELS spectra in a wide loss energy range of 2-200 eV by applying our reverse Monte Carlo method. The high accuracy of the obtained optical constants is justified with the ps- and f-sum rules. We found that our present optical constants of amorphous carbon fulfill the sum rules with the highest accuracy compared with the previously published data. Therefore, we highly recommend to replace the previous data with the present ones for practical applications. Moreover, we present the atomic scattering factors of amorphous carbon obtained from the dielectric function to predict its optical constants at a given density.

Interface induced diffusion.

Interface induced diffusion had been identified in a thin film system damaged by electron bombardment. This new phenomenon was observed in Al2O3 (some nm thick)/Si substrate system, which was subjected to low energy (5 keV) electron bombardment producing defects in the Al2O3 layer. The defects produced partially relaxed. The rate of relaxation is, however, was different in the vicinity of the interface and in the "bulk" parts of the Al2O3 layer. This difference creates an oxygen concentration gradient and consequently oxygen diffusion, resulting in an altered layer which grows from the Al2O3/Si substrate interface. The relative rate of the diffusion and relaxation is strongly temperature dependent, resulting in various altered layer compositions, SiO2 (at room temperature), Al2O3 + AlOx + Si (at 500 °C), Al2O3 + Si (at 700 °C), as the temperature during irradiation varies. Utilizing this finding it is possible to produce area selective interface patterning.

Electron irradiation induced amorphous SiO2 formation at metal oxide/Si interface at room temperature; electron beam writing on interfaces.

Al2O3 (5 nm)/Si (bulk) sample was subjected to irradiation of 5 keV electrons at room temperature, in a vacuum chamber (pressure 1 × 10-9 mbar) and formation of amorphous SiO2 around the interface was observed. The oxygen for the silicon dioxide growth was provided by the electron bombardment induced bond breaking in Al2O3 and the subsequent production of neutral and/or charged oxygen. The amorphous SiO2 rich layer has grown into the Al2O3 layer showing that oxygen as well as silicon transport occurred during irradiation at room temperature. We propose that both transports are mediated by local electric field and charged and/or uncharged defects created by the electron irradiation. The direct modification of metal oxide/silicon interface by electron-beam irradiation is a promising method of accomplishing direct write electron-beam lithography at buried interfaces.

Corrosion Resistance of Nanosized Silicon Carbide-Rich Composite Coatings Produced by Noble Gas Ion Mixing.

Ion beam mixing has been used to produce a silicon carbide (SiC)-rich nanolayer for protective coating. Different C/Si/C/Si/C/Si(substrate) multilayer structures (with individual layer thicknesses falling in the range of 10-20 nm) have been irradiated by Ar+ and Xe+ ions at room temperature in the energy and fluence ranges of 40-120 keV and 1-6 × 1016 ion/cm2, respectively. The effects of ion irradiation, including the in-depth distribution of the SiC produced, was determined by Auger electron spectroscopy depth profiling. The thickness of the SiC-rich region was only some nanometers, and it could be tailored by changing the layer structure and the ion irradiation conditions. The corrosion resistance of the layers was investigated by potentiodynamic electrochemical test in 4 M KOH solution. The measured corrosion resistance of the SiC-rich layers was orders of magnitude better than that of pure silicon, and a correlation was found between the corrosion current density and the effective areal density of the SiC.

Simulation of the backscattered electron intensity of multi layer structure for the explanation of secondary electron contrast.

The intensities of the secondary electrons (SE) and of the backscattered electrons (BSE) at energy 100 eV have been measured on a Ni/C/Ni/C/Ni/C/(Si substrate) multilayer structure by exciting it with primary electrons of 5, 2.5 and 1.25 keV energies. It has been found that both intensities similarly vary while thinning the specimen. The difference as small as 4 nm in the underlying layer thicknesses resulted in visible intensity change. Utilizing this intensity change, the thickness difference of neighboring regions could be revealed from the SE image. No simple phenomenological model was found to interpret the change of intensity, thus the intensity of the BSE electrons has been calculated by means of a newly developed Monte Carlo simulation. This code also considers the secondary electron generation and transport through the solid. The calculated and measured intensities agree well supporting the validity of the model.