Yes / We have synthesised osmium nanoparticles of defined size (1.5–50 nm) on a B- and S-doped turbostratic graphitic structure by electron-beam irradiation of an organometallic osmium complex encapsulated in self-spreading polymer micelles, and characterised them by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and atomic force microscopy (AFM) on the same grid. Oxidation of the osmium nanoparticles after exposure to air was detected by X-ray photoelectron spectroscopy (XPS). / We thank the Leverhulme Trust (Early Career Fellowship No. ECF-2013-414 to NPEB), the University of Warwick (Grant No. RD14102 to NPEB), the ERC (Grant No. 247450 to PJS), and the EPSRC (EP/F034210/1 to PJS). L.M.A.P., J.L., and G.C. acknowledge financial support from the EU through the ERC Consolidator Grant “VISUAL-MS”.

<p> Phosphorus (P) is a key element for maize (<em>Zea mays</em> L.) production and plays many important roles in plants. Soil-buffering of P does not allow for precise control of solution concentrations in the field, while greenhouses, growth chambers, and hydroponics provide limiting conditions. Thus, an objective of this study was to develop a practical technique for cultivating several maize plants to physiological maturity (R6) in a growth room environment, with precise control of nutrient availability and timing, and evaluate its utility for the purpose of measuring plant responses to variations in P concentration using a silica-sand-based solution culture technique. A semi-automated growth room for conducting nutrient studies on 96 maize plants was constructed and evaluated to quantify plant growth response to a range of solution P concentrations. Maize yield components were measured and compared to values for field-grown plants. Due to ideal conditions and successful simulation of light intensity, diurnal fluctuations in temperature and relative humidity, and changing photoperiod, grain yield and tissue nutrient concentrations were comparable to field-grown maize, although with greater shoot biomass. The second objective was to quantify the uptake and partitioning of nutrients as affected by P concentration at various maize growth stages. Thus, two maize hybrids were grown under both sufficient and insufficient P fertility rates using the silica-sand-based solution culture technique. Throughout the growth stages, sufficient-P plants had more than double the biomass compared to insufficient-P plants. At R1, N partitioning followed a similar pattern in both treatments, while P remobilization differed, with insufficient-P plants relying on stem tissue and sufficient-P plants remobilizing P from leaf and root tissue for grain production. Plants grown under sufficient-P fertility matured more rapidly and reached physiological maturity (R6) sooner. Sufficient-P fertility resulted in 2- to 3-fold greater grain, leaf, stem, and root biomass at R6 than insufficient-P. Nutrient partitioning patterns to plant tissues between P treatments were generally similar, except for insufficient-P plants allocating more nutrients to root tissues than sufficient-P plants. Partitioning patterns for B and Cu indicated that the high demand of maize reproductive structures for these nutrients may justify a foliar application of B and/or Cu at vegetative growth stages in some cases. The results of these studies suggests that there is great utility in further utilizing this silica-sand-based solution culture technique for more complex plant nutrient studies. </p>

The A15-based Nb3Sn and V3Ga superconducting compounds are an integral part of synchrotrons and magnetic fusion reactor technology, especially where a magnetic field higher than 10 T is required, which lies beyond the limit of conventional Nb-Ti superconductors (~8 T). These brittle intermetallic compounds are difficult to manufacture in the form of wires, required for the application purpose, using the traditional wire-drawing process. Hence, bronze technique is adopted to fabricate such filamentary wires. This is based on the solid-state diffusion where A3B compound (A=Nb or V, B=Sn or Ga) forms during the interaction of Cu(B) and A. The operation of pure superconducting wires gets restricted to the field of 12 T, however, the ever-increasing demands for an improved efficiency have promoted the development of these A15 wires with the addition of alloying elements such as Ti and Zr. Many important physical and mechanical properties of such wires depend on the growth behaviour of these compounds. Therefore, understanding the growth of such compounds necessitates an in-depth analysis on diffusion behaviour of various elements in both bronze-based solid solutions as well as A15-intermetallics. Estimation of diffusion parameters makes use of the most commonly used diffusion couple technique. There are mainly three methods available for the estimation of the interdiffusion coefficients, proposed by Matano-Boltzmann (MB), Den Broeder (dB), same as Sauer-Freise (SF) and Wagner. Among these three, MB treatment is known to be the least accurate method, especially when there is a deviation of molar volume in a system from the ideality. At the same time molar volume might affect the estimation process differently for dB and Wagner’s approach. MB method is still being used neglecting the actual molar volume variation. On the other hand, the implementation of dB or Wagner’s approach for the estimation remains to be random. For the first time, we have critically examined the role of molar volume on estimated diffusion parameters and indicated the more accurate approach. Similar analysis for the estimation of the intrinsic diffusion coefficient is conducted considering Heumann and van Loo’s methods. Furthermore, the discussion is extended to the estimations of various diffusion parameters considering the measured composition profile in the V-Ga system. A detailed diffusion study has been conducted on Cu(Ga) and Cu(Sn) solid solutions to examine the role of the vacancy wind effect on interdiffusion. The interdiffusion, intrinsic and impurity diffusion coefficients are determined to facilitate the discussion. It is found that Ga and Sn are the faster diffusing species in the respective systems. The trend of the interdiffusion coefficients is explained with the help of the driving force. Following that, the tracer diffusion coefficients of the species are calculated with and without consideration of the vacancy wind effect. We found that the role of the vacancy wind is negligible on the minor element in a dilute solid solution, which is the faster diffusing species in this system and controls the interdiffusion process. However, consideration of this effect is important to understand the diffusion rate of the major element, which is the slower diffusing species in this system. Major drawback of studying diffusion in multi-component systems is the lack of suitable techniques to estimate the diffusion parameters. In this study, a generalized treatment to determine the intrinsic diffusion coefficients in multi-component systems is developed utilizing the concept of pseudo-binary approach. This is explained with the help of experimentally developed diffusion profile in the Cu(Sn, Ga) solid solution. Based on an interdiffusion study using an incremental diffusion couple in the V-Ga binary system, we have shown that V diffuses via lattice, whereas Ga does so via grain boundaries for the growth of the V3Ga phase. We could estimate the contributions from two different mechanisms, which are, usually, difficult to delineate in an interdiffusion study. Available tracer diffusion studies and the atomic arrangement in the crystal structure have been considered for a discussion on the diffusion mechanisms. Diffusion–controlled growth rate of V3Ga at the Cu(Ga)/V changes dramatically because of a small change in Ga content in Cu(Ga). One atomic percent increase in Ga leads to more than double the product phase layer thickness and a significant decrease in activation energy. Kirkendall marker experiment indicates that V3Ga grows because of diffusion of Ga. Role of different factors influencing the diffusion rate of Ga and high growth rate of V3Ga are discussed. The growth of Nb3Sn by bronze technique on two different single crystals and deformed Nb is studied. The grain boundary diffusion-controlled growth rate is found to be different for each of these three specimens. The difference is explained on the basis of the grain size of Nb3Sn. Elemental additions such as Ti and Zr to either bronze or metal are found to improve the superconducting properties. We have examined their effects on the growth rates of A15-phase formed in Cu(B,x)/A and Cu(B)/(A,x), where x is Ti or Zr. In either cases Ti and Zr-additions result in an improved growth rate of the product phase and reduces activation energy with increase in alloying addition; however few precipitates are formed in the interdiffusion zone for Cu(B,x)/A. Wavelength dispersive spectrometry (WDS)-mapping reveals these to be x-rich. Scanning transmission electron microscopy (STEM)-analysis suggests having composition gradient inside a single precipitate. TEM-diffraction demonstrates these to be Ti(A) solid solution crystallizing as BCC-structure for Cu(B,Ti)/A. These are located on grain boundaries of A15-phase. Electron back-scattered diffraction (EBSD)-analysis demonstrates grain morphology of product phase and found the average grain size to exhibit a decreasing trend with increasing x content. Columnar grains, on Ti and Zr addition tend to form as equiaxed ones. Based on the morphology and grain size pattern, the role of grain boundary diffusion is speculated to have a dominant effect with increase in elemental additions. The texture evolution of the product phase is also investigated and found the product phase to grow as a strongly textured one with the elemental additions. A peculiar pattern is observed for the texture of the product phase and its adjacent A or A(x) grains.

Les travaux présentés dans ce manuscrit s’inscrivent dans le cadre général de la conversion et du stockage de l’énergie lumineuse. Dans ce domaine, l’utilisation de MOFs (Metal-Organic Frameworks) polyfonctionnels n’en est qu’à ses débuts et ils sont principalement utilisés sous forme de poudre cristalline. Or le développement de ces MOFs sur un support solide est essentiel dans l’obtention d’un objet technologiquement avancé répondant à des critères industriels. Les travaux réalisés lors de ce projet ont donc porté sur la croissance contrôlée de matériaux hybrides polyfonctionnels de type MOF sur une surface conductrice transparente TCO (Transparent Conductive Oxide). Les différentes fonctionnalités ont été introduites au sein du MOF par intégration d’une partie photosensible et d’une unité catalytique.A partir de systèmes de MOFs modèles à base de zirconium, il a été possible de produire des systèmes polyfonctionnels par modifications directement pendant la synthèse et/ou post synthèse. Le contrôle de la croissance, en maîtrisant les conditions expérimentales lors de la synthèse solvothermale directe in situ, nous a permis d’obtenir une couche de cristaux monodisperses solidement attachés aux supports TCO. Des efforts importants ont également été dédiés à la compréhension des mécanismes de croissance des MOF sur support TCO. Des essais de photodégradation du bleu de méthylène (polluant organique) ont permis de valider le potentiel photochimique de nos dispositifs.La méthodologie développée pour le contrôle de la croissance des MOFs à base de zirconium a été transposée avec succès à des analogues à base de titane, démontrant la portabilité de la stratégie vers d’autres types de MOFs. Ces derniers ont été utilisés en photo-réduction du CO2 lors d’essais préliminaires (collaboration avec le Collège de France) conduisant sélectivement à l’obtention de formiate. / This work is focused on the development of a functionalization method of TCO transparent conductive surfaces (Transparent Conductive Oxide) by hybrid multifunctional materials, Metal-Organic Frameworks (MOFs). Different properties are provided within the MOF by adding different photosensitive and catalytic units. The development of such materials is in its infancy and they have been mainly developed as crystalline powder. However the development of these MOFs onto a solid support is challenging but also essential toward obtaining a technologically advanced device.This project is focused on the growth controlled of MOFs crystals onto TCO support. From a Zirconium material, it was possible to obtain multifunctional systems by changing components directly during the synthesis or by post synthesis modifications. It has been possible to control the growth of materials on the support by direct in situ solvothermal synthesis and to obtain a monodisperse layer of crystals well anchored to the TCO supports. Photodegradation of methylene blue (organic pollutant) has been performed to validate their photoreactivity.The methodology developed with the Zirconium based MOF has been implemented successfully in a similar compound to include higher photosensitizer components and with titanium-based MOFs. It shows the portability of the strategy towards other types of MOFs. They were used in CO2 photo-reduction (in collaboration of the College de France) where selectively of formate production was observed.

In der vorliegenden Arbeit untersuchen wir schwache Lösungen, die zu einem geeigneten Sobolevraum gehören, q-elliptischer und parabolischer Systeme partieller Differentialgleichungen auf deren Regularität für den Fall 1 / In the present work we study the regularity of weak solution to q-elliptic and parabolic systems partial differential equations in appropriate Sobolev spaces in case 1

The electro–mechanical connection between under bump metallization (UBM) and solder in flip–chip bonding is achieved by the formation of brittle intermetallic compounds (IMCs) during the soldering process. These IMCs continue to grow in the solid–state during storage at room temperature and service at an elevated temperature leading to degradation of the contacts. In this thesis, the diffusion–controlled growth mechanism of the phases and the formation of the Kirkendall voids at the interface of UBM (Cu, Ni, Au, Pd, Pt) and Sn (bulk/electroplated) are studied extensively. Based on the microstructural analysis in SEM and TEM, the presence of bifurcation of the Kirkendall marker plane, a very special phenomenon discovered recently, is found in the Cu–Sn system. The estimated diffusion coefficients at these marker planes indicate one of the reasons for the growth of the Kirkendall voids, which is one of the major reliability concerns in a microelectronic component. Systematic experiments using different purity of Cu are conducted to understand the effect of impurities on the growth of the Kirkendall voids. It is conclusively shown that increase in impurity enhances the growth of voids. The growth rates of the interdiffusion zone are found to be comparable in the Cu–Sn and the Ni–Sn systems. EPMA and TEM analyses indicate the growth of a metastable phase in the Ni–Sn system in the low temperature range. Following, the role of Ni addition in Cu on the growth of IMCs in the Cu–Sn system is studied based on the quantitative diffusion analysis. The analysis of thermodynamic driving forces, microstructure and crystal structure of Cu6Sn5 shed light on the atomic mechanism of diffusion. It does not change the crystal structure of phases; however, the microstructural evolution, the diffusion rates of components and the growth of the Kirkendall voids are strongly influenced in the presence of Ni. Considering microstructure of the product phases in various Cu/Sn and Cu(Ni)/Sn diffusion couples, it has been observed that (i) phases have smaller grains and nucleate repeatedly, when they grow from Cu or Cu(Ni) alloy, and (ii) the same phases have elongated grains, when they grow from another phase. A difference in growth rate of the phases is found in bulk and electroplated diffusion couples in the Au–Sn system. The is explained in AuSn4 based on the estimated tracer diffusion coefficients, homologous temperature of the experiments, grain size distribution and crystal structure of the phase. The growth rates of the phases in the Au–Sn system are compared with the Pd–Sn and the Pt–Sn systems. Similar to the Au–Sn system, the growth rate of the interdiffusion zone is found to be parabolic in the Pd–Sn system; however, it is linear in the Pt–Sn system. Following, the effect of addition of Au, Pd and Pt in Cu is studied on growth rate of the phases. An analysis on the formation of the Kirkendall voids indicates that the addition of Pd or Pt is deleterious to the structure compared to the addition of Au. This study indicates that formation of voids is equally influenced by the presence of inorganic as well as organic impurities.