Abstract: Fe(2)C plays a crucial role in the precipitation of iron carbides. Jack's structural models for epsilon-Fe(2)C, and non-stoichiometric epsilon-Fe(2.4)C, are analyzed using first-principles calculations. Several new configurations of epsilon-Fe(2)C with even higher stability are found. We show how epsilon-Fe(2)C transforms into eta-Fe(2)C, and address the structural relationships with the chi-Fe(5)C(2), theta-Fe(3)C and Fe(7)C(3) phases. The relative occurrence of these phases in steel, as well as their probable evolution during tempering of quenched steels, is discussed. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Abstract: Fast degradation of in-vessel optics is one of the most serious problems for all optical diagnostics in ITER. To provide the resistance to mechanical and thermal stresses along with a high stability of optical characteristics under deposition-dominated conditions we suggest using high-reflective metallic (Ag or Al) film mirrors coated on silicon substrate and protected with thin oxide film in the divertor Thomson Scattering (TS) diagnostics. The mirrors coated with Al2O3 and ZrO2 films were tested under irradiation by deuterium ions. The experimental results on the oxide films sputtering are discussed in the context of their applicability for the first mirror protection in ITER.

Abstract: Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites are investigated using the (Pb1−zSrz)1−xFe1+xO3−y perovskites as a model system. The orientation of the CS planes in the system varies unevenly with z. A comparison of the structures with different CS planes revels that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

Abstract: Exposure to volatile organic compounds (VOCs) remains a major public health concern. Indoor VOC concentrations typically far exceed outdoor levels due to a variety of emission sources and the stringent insulation measures that are imposed today. Many attempts have been made to use photocatalysis for indoor air purification. In an ideal situation, photocatalysis is capable of complete mineralization of VOCs to H2O and CO2, without any byproduct formation. Moreover, the process can take place at standard atmospheric conditions, i.e. ambient temperature and atmospheric pressure. However, successful exploitation is still impeded due to low conversion efficiency, significant pressure loss (and hence a high energy consumption) and byproduct formation. In the first part of this thesis an attempt was made to tackles these problems by designing a novel type of photocatalytic (PCO) reactor. The PCO device consists of a cylindrical vessel filled with TiO2-coated glass tubes and equipped with UV fluorescence lamps. It was investigated in terms of fluid dynamics, coating properties, UV-light distribution and photocatalytic activity. Experimental data was later used to develop and calibrate a Multiphysics model. The model proved to be a useful tool for designing and upscaling the PCO reactor. Consequently, an optimized prototype reactor was constructed and tested according the CEN-EN-16846-1 standard for VOC removal. Although the prototype showed promising results for lab-scale conditions, it struggled with byproduct formation when purifying ppb-level VOCs. In the second part of this thesis, activated carbon adsorption was investigated in order to combine it with photocatalysis. Activated carbon fiber was opted for its fast kinetics, high adsorption capacity and thermo-electrical regeneration. The filter was studied in detail regarding the adsorption of polar and apolar VOCs at indoor air concentration levels and regeneration capabilities. Experimental data was used to develop a Multiphysics model for activated carbon adsorption as well. Consequently, a novel type of ACF filter was developed using the Multiphysics model, which was equipped with electrodes in the tips of the pleats for effective thermal regeneration. In the last part, the combination of both ACF and PCO was studied using a realistic case study. Based on the Multiphysics model, the feasibility of a so-called hybrid air purification device could be investigated. The Multiphysics model shows promising results for this hybrid PCO-ACF system and hence, a demo setup was constructed for future research.

Abstract: Experimental results show that the room-temperature carrier mobility in bulk layers of undoped or Si-doped GaN grown by LP-MOVPE on sapphire substrate shows a sudden increase as soon as the carrier density exceeds a critical value of about 10(18) cm(-3). We show that such a behavior can be theoretically reproduced by assuming that the columnar structure i.e. the dislocation microstructure is responsible for internal electronic barriers. (C) 1999 Elsevier Science B.V. All rights reserved.

Abstract: Expandable graphite of two types was synthesized by (1) hydrolysis of graphite nitrate of II stage and (2) anodic polarization of graphite in 60% HNO3. Exfoliated graphite samples were produced by thermal shock of expandable graphite samples in air at 900 °C. A comparative study of microstructural distinctions of both expandable and exfoliated graphite samples was carried out using X-ray diffraction, Raman spectroscopy, electron energy loss spectroscopy and high resolution transmission electron microscopy.

Abstract: Exfoliated graphite samples (EG) with different bulk densities were prepared by the exfoliation of expandable graphite under a thermal shock regime. As a conductive filler, EG has been incorporated successfully into the coal tar pitch matrix by mechanical mixing. The conducting behavior of the composite was interpreted based on the percolation theory. The percolation threshold of the EG/pitch conducting composites at room temperature was as low as 1.5 wt% and did not depend on the bulk density of the EG used. By means of thermogravimetry the improvement of thermal stability of the composites in comparison with pure pitches was detected. The phenomenon was ascribed to heat shielding effect of the EG particles evidenced by matrix-assisted laser desorption/ionization mass spectrometry.

Abstract: Ever since the industrial revolution, the emission of greenhouse gasses dramatically increased, resulting in high CO2 concentration in the atmosphere. The electrochemical conversion of CO2 to value added products, such as carbon monoxide, formic acid, methane, ethylene and ethanol is a very promising strategy to inhibit CO2 emissions. Nevertheless, at the moment, the electrochemical CO2 reduction (eCO2R) is not yet industrially viable, mainly due to the lack of good electrocatalysts. On the other hand, core-shell nanoparticles (NPs) have emerged over the last couple of years as promising candidates. It is believed that bimetallic enhancement effects are behind the improved performance of these core-shell NPs when compared to the individual metals. Although widely investigated, there are still some remaining issues and/or open questions. Indeed, the development of a robust and straightforward synthesis method along with fundamental insight into their resistance towards electrochemical stress remains absent. A good control over morphology, size and composition is key in determining which properties are beneficial for the eCO2R. Since these catalysts are designed to be implemented in electrolyzers, they have to maintain long-term performance. This makes the design of a reproducible method, unveiling structure-performance relationships the effect of electrochemical stress, a crucial aspect. Exploring and modifying existing synthesis methods, have led to the acquisition of a robust and reproducible synthesis method where thermal decomposition of the Cu core is combined with the galvanic replacement of Ag in organic solvents. The implementation of this method has led to the design of a wide variety of Cu-Ag bimetallic NPs and enabled to investigate their composition-selectivity profile. Introducing Ag on Cu suppressed hydrogen and increased the CO formation. CO production was boosted by using Cu@Ag core-shells and was promoted even more by changing the type of electrolyte. As these nanoparticles suffered from degradation, the 3D mapping of the structural changes of Cu@Ag core-shells under operating conditions led to the hypothesis of a two-step degradation mechanism where initially Cu leaching was observed with the subsequent sintering of the Ag shells. One approach to avoid this electrochemical degradation, investigated in this research, was the application of an ultrathin carbon layer to protect the active layer. This ultrathin carbon layer operated as a protective layer, suppressing hydrogen production and increasing the stability of the electrocatalyst. In conclusion, the product selectivity can be tuned by using different Cu-Ag bimetallic nanoparticles synthesized through a robust method. Their unique degradation pathway of Cu@Ag core-shell nanoparticles has led to the proposition of a more accurate stabilization strategy. These findings can contribute significantly in the quest for improved electrocatalysts for the eCO2R.

Abstract: Even at low temperatures, metal nanoparticles (NPs) possess atomic dynamics that are key for their properties but challenging to elucidate. Recent experimental advances allow obtaining atomic-resolution snapshots of the NPs in realistic regimes, but data acquisition limitations hinder the experimental reconstruction of the atomic dynamics present within them. Molecular simulations have the advantage that these allow directly tracking the motion of atoms over time. However, these typically start from ideal/perfect NP structures and, suffering from sampling limits, provide results that are often dependent on the initial/putative structure and remain purely indicative. Here, by combining state-of-the-art experimental and computational approaches, how it is possible to tackle the limitations of both approaches and resolve the atomistic dynamics present in metal NPs in realistic conditions is demonstrated. Annular dark-field scanning transmission electron microscopy enables the acquisition of ten high-resolution images of an Au NP at intervals of 0.6 s. These are used to reconstruct atomistic 3D models of the real NP used to run ten independent molecular dynamics simulations. Machine learning analyses of the simulation trajectories allow resolving the real-time atomic dynamics present within the NP. This provides a robust combined experimental/computational approach to characterize the structural dynamics of metal NPs in realistic conditions. Experimental and computational techniques are bridged to unveil atomic dynamics in gold nanoparticles (NPs), using annular dark-field scanning transmission electron microscopy and molecular dynamics simulations informed by machine learning. The approach provides unprecedented insights into the real-time structural behaviors of NPs, merging state-of-the-art techniques to accurately characterize their dynamics under realistic conditions. image

Abstract: Er3+Yb3+ co-doped transparent glass-ceramics with varying Er/Yb content and ratio have been prepared. High quantum yields for up- and down-conversion luminescence by energy transfer from Yb3+ to Er3+ and from Er3+ to Yb3+, respectively, have been detected and optimized with respect to the Er/Yb content and ratio, and proposed in particular for up- and down-conversion of solar spectrum for enhancement of the efficiency of solar cells. The rise and decay kinetics for the population of the excited levels of Er3+ and Yb3+ have been studied and fit. Based on these experimental data, the mechanisms for the energy transfers have been suggested with emphasis on the optimized Er/Yb content and ratio for enhancement of the efficiency of the Er3+↔Yb3+ energy transfers.

Abstract: Epitaxial thin films of GdBaCo2O5.5+δ (GBCO) grown by pulsed laser deposition have been studied as a function of deposition conditions. The variation in film structure, domain orientation, and microstructure upon deviations in the cation composition have been correlated with the charge transport properties of the films. The epitaxial GBCO films mainly consist of single- and double-perovskite regions that are oriented in different directions depending on the deposition temperature. Additionally, cobalt depletion induces the formation of a high density of stacking defects in the films, consisting of supplementary GdO planes along the c-axis of the material. The presence of such defects progressively reduces the electrical conductivity. The films closer to the stoichiometric composition have shown p-type electronic conductivity at high pO2 with values as high as 800 S/cm at 330 °C in 1 atm O2, and with a pO2 power dependence with an exponent as low as 1/25, consistent with the behavior reported for bulk GBCO. These values place GBCO thin films as a very promising material to be applied as cathodes in intermediate temperature solid oxide fuel cells.

Abstract: Epitaxial rare earth manganite thin films (ReMnO3; Re = Tb, Ho, Er, and Y) and multilayers were grown by liquid injection metal organic chemical vapor deposition (MOCVD) on YSZ(111) and the same systems were grown c-oriented on Pt(111) buffered Si substrates. They have been structurally investigated by electron diffraction (ED) and high resolution transmission electron microscopy (HRTEM). Nanodomains of secondary orientation are observed in the hexagonal YMnO3 films. They are related to a YSZ(111) and Pt(111) misorientation. The epitaxial film thickness has an influence on the defect formation. TbO2 and Er2O3 inclusions are observed in the TbMnO3 and ErMnO3 films respectively. The structure and orientation of these inclusions are correlated to the resembling symmetry and structure of film and substrate. The type of defect formed in the YMnO3/HoMnO3 and YMnO3/ErMnO3 multilayers is also influenced by the type of substrate they are grown on. In our work, atomic growth models for the interface between the film/substrate are proposed and verified by comparison with observed and computer simulated images.

Abstract: Epitaxial heterostructures of two-dimensional (2D) halide perovskites offer a new platform for studying intriguing structural, optical, and electronic properties. However, difficulties with the stability of Pb- and Sn-based heterostructures have repeatedly slowed the progress. Recently, Pb-free halide double perovskites are gaining a lot of attention due to their superior stability and greater chemical diversity, but they have not been successfully incorporated into epitaxial heterostructures for further investigation. Here, we report epitaxial core-shell heterostructures via growing Pb-free double perovskites (involving combinations of Ag(I)-Bi(III), Ag-Sb, Ag-In, Na-Bi, Na-Sb, and Na-In) around Pb perovskite 2D crystals. Distinct from Pb-Pb and Pb-Sn perovskite heterostructures, growths of the Pb-free shell at 45 degrees on the (100) surface of the lead perovskite core are observed in all Pb-free cases. The in-depth structural analysis carried out with electron diffraction unequivocally demonstrates the growth of the Pb-free shell along the [110] direction of the Pb perovskite, which is likely due to the relatively lower surface energy of the (110) surface. Furthermore, an investigation of anionic interdiffusion across heterostructure interfaces under the influence of heat was carried out. Interestingly, halide anion diffusion in the Pb-free 2D perovskites is found to be significantly suppressed as compared to Pb-based 2D perovskites. The great structural tunability and excellent stability of Pb-free perovskite heterostructures may find uses in electronic and optoelectronic devices in the near future.

Abstract: Epitaxial double perovskite La2CoMnO6 (LCMO) films were grown by metalorganic aerosol deposition on SrTiO3(111) substrates. A high Curie temperature, T-C = 226 K, and large magnetization close to saturation, M-S(5 K) = 5.8 mu(B)/f.u., indicate a 97% degree of B-site (Co,Mn) ordering within the film. The Co/Mn ordering was directly imaged at the atomic scale by scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy (STEM-EDX). Local electron-energy-loss spectroscopy (EELS) measurements reveal that the B-sites are predominantly occupied by Co2+ and Mn4+ ions in quantitative agreement with magnetic data. Relatively small values of the (1/2 1/2 1/2) superstructure peak intensity, obtained by X-ray diffraction (XRD), point out the existence of ordered domains with an arbitrary phase relationship across the domain boundary. The size of these domains is estimated to be in the range 35-170 nm according to TEM observations and modelling the magnetization data. These observations provide important information towards the complexity of the cation ordering phenomenon and its implications on magnetism in double perovskites, and similar materials.

Abstract: Enhanced weathering (EW) is an emerging carbon dioxide (CO2) removal technology that can contribute to climate change mitigation. This technology relies on accelerating the natural process of mineral weathering in soils by manipulating the abiotic variables that govern this process, in particular mineral grain size and exposure to acids dissolved in water. EW mainly aims at reducing atmospheric CO2 concentrations by enhancing inorganic carbon sequestration. Until now, knowledge of EW has been mainly gained through experiments that focused on the abiotic variables known for stimulating mineral weathering, thereby neglecting the potential influence of biotic components. While bacteria, fungi, and earthworms are known to increase mineral weathering rates, the use of soil organisms in the context of EW remains underexplored. This protocol describes the design and construction of an experimental setup developed to enhance mineral weathering rates through soil organisms while concurrently controlling abiotic conditions. The setup is designed to maximize weathering rates while maintaining soil organisms' activity. It consists of a large number of columns filled with rock powder and organic material, located in a climate chamber and with water applied via a downflow irrigation system. Columns are placed above a fridge containing jerrycans to collect the leachate. Representative results demonstrate that this setup is suitable to ensure the activity of soil organisms and quantify their effect on inorganic carbon sequestration. Challenges remain in minimizing leachate losses, ensuring homogeneous ventilation through the climate chamber, and avoiding flooding of the columns. With this setup, an innovative and promising approach is proposed to enhance mineral weathering rates through the activity of soil biota and disentangle the effect of biotic and abiotic factors as drivers of EW.