Publikationsrepositorium - Helmholtz-Zentrum Dresden-Rossendorf

Time-resolved in-situ or/and in-operando X-ray experiments open a very direct, natural way to study the formation and transformation of materials during relevant technological processes. High-brilliance, fs-pulsed X-rays generated by XFels demonstrate the highest temporal and spatial resolutions, but the maximum X-ray energy is currently limited to ~25 keV. Despite the possibility to illuminate macroscopic objects with large beams (~100mm2) synchrotron light sources produce X-rays pulses with much lower temporal resolution (~100ps), spatial coherence and brilliance but are able to reach X-ray energies higher than achieved at current FELs. MHz pulse repetition rates (ESRF:up to 5.6MHz in the 16 bunch mode) are characteristic to synchrotrons, allowing transient processes to be tracked using ultra-high-speed image acquisition systems with multiple frames, that are even able to visualize transient processes that are stochastic or a-periodic.
Here, we report on an in-situ real time investigation into high-power (>1J), ns single-pulsed (Nd:YAG, = 532 nm; pulse length ~10 ns) laser-driven irradiation processes leading either to surface ablation, crack propagation or shock generation [1] studied by a combined diffraction-direct-space-imaging experiment exploiting the single bunch structure. Whereas macroscopic changes (i.e. density changes or cracks) in bulk materials can be quite easily deduced from X-ray phase contrast imaging, information probing changes at the lattice level can be obtained using diffraction imaging.
As an example is in the figure shown such a combined experiment [2]: The first laser shot of an in-situ real-time laser hole-drilling experiment into a 0.50 mm thick Si (001) single crystalline wafer that was carried out for about 120sec. The sample was placed by about 45° with respect to the laser and the X-ray beam. Both beams intersect horizontally at the same height at an angle of 90° at the rotation center of the sample. The laser light was directed to the sample using a focusing lens. The synchronization of the cameras with laser and X-ray pulses are described in [1]. The X-ray beam fully illuminates the 10×10 mm2 wafer. The diffraction angle was tuned so that the Si (333) reflection in transmission geometry was recorded by the diffraction imaging detector.

Mass transfer limitations in multiphase reactions are a widespread phenomenon in reaction engineering. Particularly in trickle bed reactors, space-time yield is limited due to the low accessibility of the gaseous educts to the solid catalyst. The inclined rotating fixed bed reactor is a new intensification strategy for trickle bed reactors to circumvent this bottleneck. The superposition of reactor inclination and rotation results in a stratified flow, which causes wetting intermittency of the catalytic fixed bed with alternatingly unhindered access of gas and liquid educts to the catalyst. The conversion for the α-methylstyrene hydrogenation has been doubled with the new reactor concept compared to the trickle bed operation, which highlights the potential of the process intensification strategy [1].
Within a DFG-funded project, a feasible model approach for the prediction of the space-time yield of the process intensification strategy is developed. In order to identify the most beneficial process windows and proper design parameters, a reactor model framework consisting of a two-phase Eulerian-Eulerian model and a heterogeneous continuum model to describe the hydrodynamics and to capture mass transfer and reaction phenomena, respectively, is proposed. In this contribution, the heterogeneous one-dimensional continuum model accounting for intraparticle gradients with time-dependent Neumann boundary conditions at particle scale is implemented. While the catalyst wetting intermittency leads to dynamic species concentrations at the particle scale, the species concentrations of the liquid bulk phase are stationary. Coupling of the different scales is realized by a two-way approach, using the species concentrations on each scale. The implemented model is applied for simulation studies considering the hydrogenation of α-methylstyrene to cumene in order to investigate the influence of period length via reactor rotation velocity and the wetting/draining cycle via flow stratification defined as split on the space-time yield.

The major goal of the iCross project is to link experimental results and reactive transport modelling across scale to get a fundamental understanding of processes in the multi barrier system of a potential nuclear waste repository. This poster shows how the mapping of surface topography via vertical scanning interferometer results in quantitative information about the surface reactivity. Furthermore, it highlights how Positron emission tomography can be used to characterize transport patterns in geomaterials.

The development of new materials is today closely related to the “creation” of new functional nano structures. Structural investigations are the key to establish a connection between the functional and structural properties generating these functions. This knowledge makes it possible to design new materials with precisely predetermined properties. The function of nano structures is not only determined by their internal structure, but in large part by their morphology and surface properties.

Time-resolved in-situ or/and in-operando X-ray experiments open a very direct, natural way to study the formation and transformation of materials during the relevant technological processes. The talk will build a bridge from classical material science problems, like the formation of 3-dimensional Germanium nano crystal arrays embedded in a dielectric matrix using synchrotron radiation, or the crystallization process during a rapid thermal annealing (RTA) of an amorphous GeSn thin film using a laboratory setup, to experiments exploiting a µsec-time resolution and even behind that.

For example, material processing by laser beams is a widely used technology in industry. Many applications, like the fabrication of thin solar cells, require a large area processing in short times with a limited heat exposure. Therefore time resolved studies of laser driven processes are again of great scientific interest. If thousand of frames are needed to follow the materials evolution on an atomic level the regular bunch structure of a synchrotron source turns out to be an ideal probe to sense changes in the morphology and crystal structure during and after a laser-sample(target) interaction.

Nanometer probing of ultrahigh intensity ultrashort pulse laser interaction with solid density plasmas, by SAXS using XFELs

The ability to manipulate the metal-insulator transition (MIT) of metal oxides is of critical importance for fundamental investigations of electron correlations and practical implementations of power efficient tunable electrical and optical devices. Most of the existing techniques including chemical doping and epitaxial strain modification can only modify the global transition temperature, while the capability to locally manipulate MIT is still lacking for developing highly integrated functional devices. Here, lattice engineering induced by the energetic noble gas ion allowing a 3D local manipulation of the MIT in VO2 films is demonstrated and a spatial resolution laterally within the micrometer scale is reached. Ion-induced open volume defects efficiently modify the lattice constants of VO2 and consequently reduce the MIT temperature continuously from 341 to 275 K. According to a density functional theory calculation, the effect of lattice constant variation reduces the phase change energy barrier and therefore triggers the MIT at a much lower temperature. VO2 films with multiple transitions in both in-plane and out-of-plane dimensions can be achieved by implantation through a shadow mask or multienergy implantation. Based on this method, temperature-controlled VO2 metasurface structure is demonstrated by tuning only locally the MIT behavior on the VO2 surfaces.

Presentation of past and ongoing campaigns aimed at the efficient generation of high energy proton beams at the Draco PW laser facility of Helmholtz-Zentrum Dresden - Rossendorf (HZDR).

We investigate the mechanical properties of freely suspended nanostrings fabricated from tensilestressed, crystalline In1-xGaxP. The intrinsic strain arises during epitaxial growth as a consequence of the lattice mismatch between the thin film and the substrate, and is confirmed by x-ray diffraction measurements. The flexural eigenfrequencies of the nanomechanical string resonators reveal an orientation dependent stress with a maximum value of 650 MPa. The angular dependence is explained by a combination of anisotropic Young's modulus and a change of elastic properties caused by defects. As a function of the crystal orientation, a stress variation of up to 50% is observed. This enables fine tuning of the tensile stress for any given Ga content x, which implies interesting prospects for the study of high Q nanomechanical systems.

We report on indirect X-ray detector systems for various full-field, ultra high-speed X-ray imaging methodologies, such as X-ray phase-contrast radiography, diffraction topography, grating interferometry and speckle-based imaging performed at the hard X-ray imaging beamline ID19 of the European Synchrotron - ESRF. Our work highlights the versatility of indirect X-ray detectors to multiple goals such as single synchrotron pulse isolation, multiple-frame recording up to millions frames per second, high efficiency, and high spatial resolution. Besides the technical advancements, potential applications are briefly introduced and discussed.

This presentation provides an overview of current concepts of MVT deposit formation. As an in-depth case study, MVT-style deposits in South Africa are used to illustrate variations to the common theme.

Extending from Northern America to Central China the Variscan belt is a Paleozoic Orogen exceptionally well endowed in magmatic-hydrothermal ore deposits, including skarn deposits. Yet, the genesis of fertile skarns and their distinction from barren equivalents in orogenic zones is only poorly constrained. Here, we present innovative U-Pb laser-ablation inductively-coupled-plasma mass-spectrometry geochronology of garnet from different skarns in the Erzgebirge, a classic metallogenic province in central Europe. Garnet ages obtained not only constrain the timing of fertile skarn formation and associated Sn, W, Fe, Zn, Cu and In mineralization, but also clearly distinguish these from barren skarn bodies. We show that barren skarns formed during times of peak regional metamorphism at ∼340 Ma whereas mineralized skarns are temporally associated with late-orogenic magmatism at ∼325-313 Ma as well as post-orogenic magmatism at ∼308-295 Ma. The recognition of discrete mineralization events associated with the largest and economically most important skarn deposits provides valuable insight into the punctuated evolution of magmatic-hydrothermal systems in ancient collisional orogens on a regional scale; this has important implications to direct future mineral exploration.

Much of the basement geology of Central Europe is characterized by volcanosedimentary successions of Late Precambrian and Early Paleozoic age that have been variably deformed and metamorphosed during the Variscan orogeny, followed by the intrusion of voluminous granites. The Variscan orogen records the closure of the Rheic ocean and the collision of Laurussia with Gondwana to form the Supercontinent Pangaea, and occurred as a series of protracted geotectonic events providing a suitable framework for the formation of a diverse range of ore deposits.

It comes as no surprise that the Variscan basement is host to most significant ore deposits of Central Europe. These ore deposits did not only provide the raw materials needed for industrial development in the past, but their mining yielded the need for scientific research and technological innovation. This need was also expressed by the publication of the world’s first textbook dedicated to economic geology as a distinct subdiscipline of the geosciences (Cotta 1855).

Industrial exploitation of most ore deposits of the Variscan basement in Central Europe ceased towards the end of the 20th century, typically due to subdued metal prices, but not motivated by a lack of mineral resources. Yet, following the demise of the mining sector there was the prevailing perception that Central Europe had little to offer for future exploration. This erroneous perception has seen a surprising reversal in the last decade. Renewed exploration interest is attributable not only to higher commodity prices but also to the realization of the significant geostrategic risk of highly industrialized countries to be entirely dependent on raw materials imports (EU 2008).

In metallurgy, gas-stirring ladle treatment of aluminum alloys and steels is applied for the control of non-metallic inclu-sion population. The intense mixing of the molten metal bath by the bubbly flow provides the agglomeration of strongly dispersed solid inclusions and subsequently, the entrapment of agglomerates by gas bubbles floating up into the slag.
This work focuses on flow-induced particle agglomeration in liquid metal. We perform model experiments to study particle-laden liquid metal flow around a circular cylinder. The fluid flow is driven by an electromagnetic induction pump. Neutron transmission radiography is employed for time-resolved visualization of the particle trajectories in the opaque liquid metal.
The experimental setup is designed as a closed liquid metal loop shown in Figure 1a. The flat channel, made of welded stainless steel, has a rectangular inner cross section with 3 mm depth, i.e. parallel to neutron beam direction, and 30 mm width. A 5 mm diameter cylindrical obstacle representing a single rising bubble is placed in the mid-dle of the straight channel section. The disk-type rotating permanent magnet induction pump is locat-ed at the lower U-shaped channel section. By controlling the pump rotational speed in the range of 15…95 min-1, the average flow velocity of 6…40 cm/s results during the measurements.
Low-melting gallium alloyed with 7 wt-% tin (Ga-Sn) is employed as model liquid metal, so that the experimental setup can be operated at room temperature without additional heating. Gadolinium(III) oxide particles (Gd2O3) in a grain size range of 400-600 µm serve as model particles, since they have superior attenuation characteristics for neutron radiation compared to the liquid metal. To introduce the solid Gd2O3 particles into the liquid Ga-Sn, a two-step mixing protocol is developed. It includes the initial preparation of a paste-like suspension with high solid content of wetted particles, followed by a second mixing step inside the Ga-Sn-filled channel by means of the electromagnetic pump. In-creased rotational speed up to 550 min-1 combined with changing rotating direction is applied for in-tense stirring and distributing the particles homogenously in the liquid metal.
The neutron imaging studies are performed at the SINQ beamlines NEUTRA and ICON at the Paul Scherrer Institute, Villigen, Switzerland. By imaging with both high spatial (0.1 mm/px) and temporal (100 fps) resolution, the fast-moving particles are captured as single objects. In terms of en-hanced contrast-to-noise ratio between the Gd2O3 particles and the surrounding liquid Ga-Sn, the currently best neutron image quality is achieved on the ICON beamline due to the higher beam aper-ture (80 mm) yielding the maximum neutron flux of 1.4 x 108 cm-2 s-1 mA-1. The neutron transmission image sequences provide raw data on particle positions and motion in the liquid metal loop, in particular in the shear flow around the cylindrical obstacle. By image processing and data analyzing, we investigate the particle behavior depending on various fluid flow rates.

In this study three hydrometallurgical methods are described for leaching of a eudialyte concentrate with H2SO4: (i) direct leaching, (ii) fast leaching and (iii) water leaching of dehydrated acid/concentrate mixture. It is demonstrated how to obtain a silica free solution, how parameter variations impact the properties of precipitated silica and which processes lead to losses of valuable components during leaching. Furthermore, the acid solubility of gangue minerals in the concentrate is analyzed and the resulting consequences in terms of leach solution contamination and acid consumption are discussed. The best result in terms of the average yield of value components (REEs, Zr(+Hf), Mn and Nb) of 86 % is obtained by direct leaching under mild conditions (cH2SO4=1 mol/L; TL=60 °C). However, released silicic acid does not precipitate and aggregates at pulp density ϱPD,L=100 kg/m3 by gelling. Fast leaching allows the efficient removal of silica at high solid-liquid ratios in the pre-treatment stage. Due to mass transfer limitations, high efficiency stirrers are crucial for achieving high yields in short reaction times. Dehydration of the acid/concentrate mixture before water leaching can be a good alternative if well-defined amount of acid is used; however, high energy input is needed.

Selten-Erd-Elemente (SEE) sind 17 verschiedene Elemente (Scandium, Yttrium sowie die sog. Lanthanoide), die weltweit in nur wenigen Regionen in abbauwürdigen Mengen zu finden sind. SEE gelten als Schlüsselkomponenten der Hightech-Industrie und werden unter anderem in Windturbinen, Smartphones und Energiesparlampen eingesetzt.

In metallurgy, the achievement of inclusion cleanliness is a major challenge for the production of high-performance structural and functional metallic materials like aluminium alloys and steels. Ladle treat-ment of molten metal by gas injection has been employed for a long time as the processing stage is mainly responsible for the control of non-metallic inclusions in metal alloys. In these ladles, inclusion are separated by the combination of settling down and floating up. Since bigger inclusion aggregates are eliminated more easily, agglomeration is supposed to play an essential role. In case of the floata-tion process, the probabilities of collision as well as attachment between gas bubbles and solid in-clusions is strongly dependent on their sizes.
This work is focussed on the visualization of three-phase particle-laden liquid metal flow in model experiments, applying 2D X-ray and neutron transmission imaging. Low-melting gallium-based alloys are employed for the imaging studies at room temperature. Modell particles containing tungsten and gadolinium are used due to their excellent attenuation characteristics for polychromatic X-ray and thermal neutrons, respectively. Injection of inert argon gas drives the liquid metal flow in a rectangular shaped vessel having a gap size of up to 20 mm. For both X-ray and neutron imaging, the time-resolved measurements are performed by means of a scintillation screen in combination with a sCMOS camera. The captured trajectories of rising millimetre-sized gas bubbles and submillimetre-sized solid particles, carried by the bubbly liquid metal flow, are analysed regarding bubble - particle and particle - particle interactions.

The helium ion microscope has already proven its value for high-resolution imaging, composition analysis, nanofabrication, and material modification. However, imaging in transmission mode remains not fully explored. Mass-thickness contrast has been studied using a conversion plate below the specimen and collecting secondary electrons with an ET detector. Changing from bright to dark field regime was demonstrated using an annular microchannel plate and changing the acceptance angle by adjusting the distance between the sensor and the sample. Channeling and diffraction phenomena provide information about the crystal structure and can be recorded by a position-sensitive detector. In this report, we present our approach to explore this imaging mode, the challenges and main figures of merit. Our test setup with a position-sensitive detector will be shown, and simulations of the contrast mechanism will be presented.

Siderophores are biomolecules, which can form strong complexes with different metals. They are produced by microorganisms and a biotechnological production of these chelators offers an application in different processing methods. Particularly amphiphilic siderophores are very interesting for the froth flotation process. The hydrophilic part, carrying hydroxamate groups is responsible for the binding of the metals. Flotation agents produced by the chemical industry with the same functional groups have already been applied successfully in this processing method. It can be suggested, that siderophores carrying the same functional groups, also work well as collectors. The fatty acid tail, that is representing the hydrophobic part, gets in contact with the bubbles and avoid additional chemicals and further working steps for making the target mineral particles hydrophobic. The aim of this study is to show the usage of amphiphilic siderophores in froth flotation process in different scales and with different minerals.

We proposed and demonstrated a method to enhance photoresponses in the timescale from nanoseconds to microseconds of an all optically driven VO₂-based terahertz (THz) wave modulator by driving the initial VO₂ close to percolation threshold (via externally heating the initial VO₂ thin film near insulator-to-metal transition temperature). We experimentally realized 10-fold, 3-fold, and 3-fold improvement of photosensitivity, photoresponsivity, and optical modulation bandwidth of the VO₂-based THz wave modulator, respectively. Percolation theory, along with the macroscopic conductivity response, was used to explain the mechanism for photomodulation response enhancement. The enhanced photomodulation response is promising especially for optical modulators and photodetectors. This approach is also compatible with other optimization methods and can be further used to enhance other VO₂-based optoelectronic devices.

The complexation of the trivalent lanthanides Nd(III) and Eu(III) and of the actinide Am(III) with malate was studied using a multi−method approach. The combination of structural and thermodynamic studies was required for the interpretation of the stoichiometry and thermodynamic data (logβ0, Δ_rH⁰ _m,2, Δ_rS⁰ _m, Δ_rG⁰ _m) of the lanthanide/actinide malate complexes leading to a profound molecular understanding of the system. The structure-sensitive methods vibrational spectroscopy and extended X–ray absorption fine structure spectroscopy complemented with quantum-mechanical ab–initio molecular dynamics calculations revealed a tridentate ring structure of the respective metal complexes. The metal is coordinated by two carboxylate groups and a hydroxyl group. UV–Vis, laser fluorescence and calorimetric studies consistently yielded two complex species having a 1:1 and a 1:2 (metal:malate) stoichiometry. Parallel factor analysis and iterative transformation factor analysis were applied to decompose experimental spectra into their single components and to determine stability constants. The 1:1 and 1:2 Nd(III) malate complexation constants determined by isothermal titration calorimetry were extrapolated to zero ionic strength using the specific ion interaction theory, yielding logβ₁ ⁰ and logβ₂ ⁰ of about 6 and 9, respectively. The respective complexation enthalpies Δ_rH⁰ _m,1 and Δ_rH⁰ _m,2 showed average values of 5 kJ·mol⁻¹ which are typical for small organic molecules. The comparison of Nd(III) and Am(III) malate complexes showed that the malate binding motif, the speciation and the thermodynamics can be transferred from lanthanides(III) to actinides(III) supporting the 4f–/ 5f–element homology.

Concrete widely serves as an engineering barrier and for waste conditioning in nuclear waste re-positories. Organic additives like poly(hydroxyl)carboxylates are commonly used for tuning the physico-chemical and mechanical properties of fresh concrete. In the worst-case scenario of wa-ter intrusion into the waste repository, the concrete may degrade, so that the soluble organic ad-ditives will be leached out and may form stable radionuclide (RN) complexes. Consequently, for a long-term risk assessment in nuclear waste repositories, the interactions of RNs with cement additives and CSH phases (main phase of cement) must be known. Americium(III) is one of the RN that will determine the radiotoxicity of a waste repository for a long time. As a model com-pound for cement additives malic acid (α-hydroxydicarboxylic acid) was chosen...

Pancreatic ductal adenocarcinoma (PDAC) stroma, composed of extracellular matrix (ECM) proteins, promotes therapy resistance and poor survival rate. Integrin-mediated cell/ECM interactions are well known to controls cancer cell survival, proliferation and therapy resistance. Here, we identified β8 integrin in a high-throughput knockdown screen in three-dimensional (3D), ECM-based cell cultures for novel focal adhesion protein targets as critical determinant of PDAC cell radiochemoresistance. Intriguingly, β8 integrin localizes with the golgi apparatus perinuclearly in PDAC cells and resection specimen from PDAC patients. Upon radiogenic genotoxic injury, β8 integrin shows a microtubule-dependent perinuclear-to-cytoplasmic shift as well as strong changes in its proteomic interactome regarding the cell functions transport, catalysis and binding. Parts of this interactome link β8 integrin to autophagy, which is diminished in the absence of β8 integrin. Collectively, our data reveal β8 integrin to critically co-regulate PDAC cell radiochemoresistance, intracellular vesicle trafficking and autophagy upon irradiation.

Concrete widely serves as an engineering barrier and for waste conditioning in nuclear waste re-positories. Organic additives like poly(hydroxyl)carboxylates are commonly used for tuning the physico-chemical and mechanical properties of fresh concrete. In the worst-case scenario of wa-ter intrusion into the waste repository, the concrete may degrade, so that the soluble organic ad-ditives will be leached out and may form stable radionuclide (RN) complexes. Consequently, for a long-term risk assessment in nuclear waste repositories, the interactions of RNs with cement additives and CSH phases (main phase of cement) must be known. Americium(III) is one of the RN that will determine the radiotoxicity of a waste repository for a long time. As a model com-pound for cement additives malic acid (α-hydroxydicarboxylic acid) was chosen...

In recent years Focused Ion Beam (FIB) processing has been developed into a well-established and promising technique in nearly all fields of nanotechnology for patterning and prototyping on the µm-scale and below. Liquid Metal Alloy Ion Sources (LMAIS) represent a promising alternative to expand the FIB application fields beside all other source concepts. The need of light elements like Li was investigated using various alloys. A promising candidate is a Ga35Bi60Li5 based LMAIS which is introduced in more detail and operates stable for more than 1000 µAh. It enables high resolution imaging and patterning using Li and sample modification using Ga or heavy polyatomic Bi clusters, all coming from one ion source.

Uranium is widespread in the environment, resulting both from natural occurrences and anthropogenic activities. Its toxicity is mainly chemical rather than radiological. In the blood it is transported as uranyl UO22+ cation and forms complexes with small ligands like carbonates and with some proteins. From there it reaches the skeleton, its main target organ for accumu lation. Fetuin is a serum protein involved in biomineralization processes which was demonstrated to be the main UO22+‐binder in vitro. Fetuin’s life cycle ends in bone. It is thus suspected to be a key protagonist of U accumulation in this organ. Up to now, there has been no effective treatment for the removal of U from the body and studies devoted to the interactions involving chelating agents with both UO22+ and its protein targets are lacking. The present work aims at studying the potential role of the 3,4,3‐LI(1,2‐HOPO) as a promising chelating agent in competition with fetuin. The apparent affinity constant of the 3,4,3‐LI(1,2‐HOPO) was first determined, giving evidence for its very high affinity similarity to that of fetuin. Chromatography experiments, aimed at identifying the complexes formed and quantify their UO22+ content, and spectroscopic structural investigations (XAS) were carried out, demonstrating that the 3,4,3‐LI(1,2‐HOPO) inhibits/limits the formation of fetuin‐uranyl complexes in stoichiometric conditions. But surprisingly, possible ternary complexes stable enough to remain present after the process, were identified for sub stoichiometric conditions of HOPO versus fetuin. These results contribute to the understanding of the mechanisms accounting for U residual accumulation despite the chelation therapy after internal contamination.

Short introduction to general principles for the statistical analysis of mineral chemistry data.

Any data measured (or reported) in terms of proportions of a whole is called ‘compositional’. Virtually all geochemical data falls under this category. Because such data has a number of special properties, specific procedures are required for its statistical analysis. Generally, it cannot be meaningfully analyzed by methods designed for the analysis of multivariate Gaussian data, such as the standard regression analysis still used by many geologists.

This lecture is intended to give a brief overview of the most important mathematical characteristics of compositional data, and what consequences these have for the statistical analysis of such data. It will provide the theoretical foundations for the next lecture(s) in which the specific problems associated to the analysis of mineral chemistry data (lecture 2) and hierarchical data structures (lecture 3) will be considered in somewhat more detail. These later two lectures are intended as more practical guides to actual data analysis.

Sustainable source of energy is the emergent necessity for the near future which comes from the simultaneous two issues: The growing request for energy and the necessity to strictly limit and control carbon emissions with warning on global warming. Although there are very terrible statistics of CO2 emission worldwide (110 billion metric tonnes in 2010 with estimated 140 billion metric tonnes by 2035), there are also hopes in that the plants and biomasses may sequester more than 260 Giga tonnes of CO2 annually. Interestingly, approximately 183 Giga tons of CO2 are annually fixed through microalgae to produce about 100 Giga tons of its biomass. These are other great motivations to invest in microalgae-based technologies such as microbial fuel cell (MFC) which are the cells to produce power from simultaneous CO2 sequestration and wastewater treatment. In this chapter, we present an overview of the current status together with the future prospects on the fuel cells based on biomass. Additionally, the necessities for scaling up the MFCs have been discussed. The main motivation for research and developments in this field is highlighted to develop green energy and technology for environmental protection. Specifically, latest researches and achievements in MFC technology are presented. The main constituents of MFC, i.e. anodes, cathodes, substrates, and microorganisms are discussed with the latest researches and developments. As a rule of thumb, for scale-up purposes, there is a threshold volumetric power density of 1 kWm-3, maintaining of which as the lab-scale one is challengeable. However, there are suggestions such as optimizing some key factors, such as and appropriately spacing the electrodes with the specific surface area. In this regard, three-dimensional electrodes with highly surface area for enhanced microbial attachment and anodic performance such as tenuous graphite rods have been introduced.

Дискретное быстрое преобразование Фурье (БПФ) позволяет рассчитывать временную эволюцию электромагнитных полей без численной дисперсии и дает ряд других преимуществ, существенных при численном моделировании некоторых физических процессов. Однако существенная нелокальность обработки данных при выполнении БПФ ограничивает возможности создания эффективных, хорошо масштабируемых суперкомпьютерных реализаций этого подхода. В работе проводится анализ перспектив эффективного распараллеливания вычислений на основе локального применения БПФ в пространственных доменах с перекрытиями, позволяющими согласованно переносить все возмущения между доменами за счет ограниченности скорости распространения электромагнитных возмущений.

We investigate the hopping transport of positively charged mobile oxygen vacancies V(o)(+)in electroforming-free bipolar memristive BiFeO3 switches by conducting impedance spectroscopy and quasistatic state-test measurements. We demonstrate that BiFeO3 switches with mobile oxygen vacancies (V-o(+)) and fixed substitutional Ti4+ donors on Fe3+ lattice sites close to the bottom electrode have a rectifying top electrode with an unflexible barrier height and a rectifying and/or nonrectifying bottom electrode with a flexible barrier height. The field-driven hopping transport of the oxygen vacancies determines the recon- figuration of the flexible barrier and the dynamics of the resistive switching. Average activation energies of 0.53 eV for trapping and of 0.31 eV for the release of oxygen vacancies by the Ti4+ donors during application of the SET and RESET excitation pulses are extracted, respectively. The larger activation energy during SET is experimentally verified by impedance spectroscopy measurements and evidences the local enhancement of the electrostatic potential profile at the bottom electrode due to the Ti4+ donors on Fe3+ lattice sites.

Many flotation kinetics models have been studied in the literature. Their applicability was extensively investigated and argued in detail. However, model selection criteria were not adequately discussed from the statistical points of view. In this investigation, the kinetic behavior of a complex copper sulfide ore was studied in a mechanical Denver flotation cell focusing on flotation kinetics of chalcopyrite, pyrite and molybdenite. Different flotation kinetics models including nine common empirical models and four mathematical models namely Hill, Chapman (Sigmodial function), single rectangular (Hyperbola equation) and exponential were applied to the experimental data. In addition to assessment of the goodness of fit criterion for each model, a factor of model complexity was considered using information criteria (IC) (i.e. Bayesian information (BIC), low of iterated logarithm (LILC) and Akaike information (AIC) indices). The obtained results showed that the IC indices could simply manifest the best-fitted model to the experimental data. Whereas, the coefficient of determination values (R2) were relatively same for all models. By taking the R2 and model complexity criteria into account, the exponential model was chosen as the best representative mathematical model to demonstrate chalcopyrite kinetic behavior. However, Chapman model was selected as the best one for the flotation of pyrite and molybdenite. In case of the common first-order flotation kinetics models, fast and slow flotation kinetic model (Kelsall) was reasonably fitted the best to the given data of chalcopyrite. However, the gas/solid kinetics adsorption model was chosen as the best-fitted one for pyrite and molybdenite. Furthermore, it was found that mathematical models represent better results in association with flotation kinetic behavior of chalcopyrite, pyrite and molybdenite due to the consideration of more parameters in modeling. Finally, it was concluded that the IC indices must be applied to the process of model selection due to consideration of goodness of fit, complexity of a model and model consistency.

Particle-bubble sub-processes cannot be directly and physically obtained in froth flotation due to the complexity of the process as well as numerous and dynamic interactions of particles and bubbles in an extremely intensive turbulent condition. Therefore, over the last three decades, two fundamental model configurations have been used as an only solution for prediction of particle-bubble collection efficiencies (E-coll). Additionally, the relative intensity of the main flotation parameters on flotation rate constant, particle-bubble interactions together with their interrelations is not adequately addressed in the literature.

The present study attempts in two separate phases to overcome these difficulties. In the first stage, prediction and evaluation of particle-bubble sub-processes are critically discussed by categorizing them in two configurations. The analytical models (approach I) commonly applied generalized Sutherland equation (E-c(GSE)), modified Dobby-Finch (E-a(DF)) and modified Schulze stability (E-s(SC) ) models. The second approach, numerical models, utilized Yoon-Luttrell (E-c(YL)), Yoon-Luttrell (intermediate) (E-a(YL)) and modified Schulze stability (E-s(SC)) models. In the second stage, relative intensity and interrelation of key effective hydrodynamic parameters on the probability of particle-bubble encounter (E-c) and flotation rate constant (k) are obtained and optimized by mea s of the response surface modeling (RSM) based on central composite design (CCD). Five key factors including particle size (1-100 mu m), particle density (1.3-4.1 kg/m(3)), bubble size (0.05-0.10 cm) and bubble velocity (10-30 cm/s) together with turbulence dissipation rate (18-30 m(2)/s(3)) are considered in order to maximize the responses including the k and E-c.

The results obtained show that the E-coll calculated by numerical techniques (configuration (II)) is greater than that of analytical approaches (configuration (I)) due to assumptions involved in using Yoon-Luttrell collision and attachment models. It is also found that under the conditions studied, particle size and bubble velocity are the most effective factors on E-c and k, respectively. Furthermore, not only the relative significance of factors on E-c and k but also the interrelation of cell turbulence and bubble size as well as bubble velocity and turbulence are shown to be inconsistent in the literature and thus require further studies. We briefly reported the main longstanding challenges in flotation kinetic modeling and emphasized on a serious need for fulfilling lack of physical observations. Finally, the presented analyses with respect to three-zone model offer a new concept for the extension of common flotation modeling approach using analytical and numerical techniques.

Fine particle separation is a challenging task and relies on a proper understanding of interfacial properties. In our research the focus lies on the process of flotation, which is a heterocoagulation separation method for fine particles in aqueous dispersions (size range approx. 5 µm < x <200 µm). It has been used in large extent for several decades and with billions of tons of particles processed per annum in the mining industry to separate valuable mineral particles from worthless ones. The main principle of separation is the particles' differences in wettability. This wettability is influenced by controlled selective adsorption of amphiphilic molecules rendering most typically the valuable containing minerals hydrophobic. Usually the particle property "wettability" is being quantified with a water contact angle. However, this value is not only difficult to assess for particles but furthermore through Young's equation a function of the surface free energy, which is a complex parameter as a result of various interatomic/intermolecular interactions. Using iGC we show how to characterize these complex wettability properties of particles assessing the heterogeneity of disperse and acid base specific surface free energies. These complex values are used in accordance to an approach by van Oss to formulate a new wettability parameter for flotation which is the specific free energy of interaction between a particle and a gas bubble immersed in water. We are presenting the general approach and results from various mineral collector systems and give insights to the boundary conditions and the general calculation scheme. In a recent trial we show the predictive power of the results. Furthermore we show how iGC can be put in context to other interaction investigations using flotability, contact angle measurements and colloidal probe atomic force microscopy.

The MgAl(Sn) layered double hydroxides (LDH) with the atomic ratios Mg/(Al+Sn) = 3 and Sn/(Sn+Al) = 0, 0.002, 0.005, 0.01, 0.05, 0.1, 0.3, 0.5, 0.7, 1.0 were synthesized and the ratio Sn/(Sn+Al) ≤ 0.1 was shown to provide the formation of systems with uniform phase composition. Mixed oxides derived from LDH retain the high specific surface area of 150-200 m2/g and the basic properties when some aluminium atoms are replaced with tin. It was found that the Sn-containing mixed oxides are able to restore the layered structure during rehydration and intercalate the anion precursors of platinum into the interlayer space of the formed LDH.
The emerging platinum sites initiate the reduction of tin at temperatures below 723 K. TEM, EXAFS and XPS studies demonstrated that tin introduction in the support increases the dispersion of supported platinum. An extreme dependence of the activity of Pt/MgAl(Sn)Ox catalysts in propane and n-decane dehydrogenation on the tin content in the support was revealed. The active catalysts are characterized by the phase and elemental uniformity of the support, highly disperse state of Pt(0), and the absence of a noticeable amount of reduced tin and bimetallic particles.

Flotation is one of the feasible separation methods suggested for recovery of petroleum coke from the tailings of lime calcination furnaces. In this study, analyses of ash content and calorific value of petroleum coke in lime calcination tailings were used to measure its floatability and product quality. In addition, seven most common flotation kinetics models were fitted to the obtained experimentalm data. Based on the maximum recovery, minimum ash content, and maximum calorific value of the flotation products, optimum dosages for collector (kerosene) and frother (MIBC) were found 30 g/t and 60 g/t, respectively. Regarding the flotation kinetic modeling and the obtained sum of squared errors (SSEs), Agar and Klimpell models were found to have the best and the poorest fits to the experimental data, respectively. Finally, it was concluded that new statistical concepts such as information criteria (IC) and non-linear generalized least squares estimation (NLGLSE) must be applied to the process of model selection owing to consideration of goodness of fit, complexity of a model and model consistency.

Today: Limits in simulating stratified & segregated two phase flow
Algebraic Interfacial Area Density Model (AIAD)
Free Surface Drag
Turbulence Damping
Sub-grid wave turbulence (SWT)
Verification and Validation is going on – more experimental data are required for the validation

Surface-modulated magnonic crystals are the natural link between continuous films with sinusoidal spin-wave eigenmodes and one-dimensional magnonic crystals composed of individual nanowires. Nevertheless, the transformation process of the spin-wave modes in this transition remains yet unclear. Here, spin-wave modes in their entire transition from a flat film to a ‘full’ (one-dimensional) magnonic crystal are studied by ferromagnetic resonance (FMR) and micromagnetic simulations. For this purpose, the surface of a pre-patterned thin permalloy film was sequentially ion milled resulting in hybrid structures, referred to as surface-modulated magnonic crystals, with increasing modulation depth. After each step, FMR measurements were carried out in backward-volume and Damon-Eshbach geometry. The evolution of each spin-wave resonance is studied together with the corresponding mode profile obtained by micromagnetic simulations. Simple rules describing the transition of the modes from the film to the modes of the full magnonic crystal are provided unraveling the complexity of spin-wave states in these hybrid systems.

Long-range spin transport in magnetic systems can be achieved by means of exchange-mediated spin textures with robust topological winding - a phenomenon referred to as spin superfluidity. Its experimental signatures have been discussed in antiferromagnets which are nearly free of dipolar interaction. In ferromagnets, which present with non-negligible dipole fields, however, realization of such spin transport has remained a challenge. Using micromagnetic simulations, we investigate exchange-mediated spin transport in extended thin ferromagnetic films. We uncover a two-fluidstate, in which the long-range spin transport by spin textures co-exists with and is stabilized by spin waves, as well as a soliton-screened spin transport regime at high spin injection biases. Both states are associated with distinct spin texture reconstructions near the spin injection region and sustain spin transport over large distances.

Recent experiments have demonstrated transport and separation of hydrogen isotopes in layered materials, such as hexagonal boron nitride and molybdenum disulphide. Here, based on first-principles calculations combined with well-tempered metadynamics simulations, we report the chemical interactions and mobility of protons (H+) and protium (H atoms) in the interstitial space of these layered materials. We show that both H+ and H can be transported between the layers of h-BN and MoS2 with low free energy barriers, while they are immobilized in graphite, in accordance with the experimental observations. In h-BN and MoS2, the transport mechanism involves a hopping process between the adjacent layers, which is assisted by the low- energy phonon shear modes. Defects present in MoS2 suppress the transport and act as traps for H species.

The DNA origami method provides a programmable bottom up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nano-electronics and nano-photonics device fabrications. This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanomolds and nanosheets are used for the fabrication of nano-electronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanomolds and nanosheets create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanomold and nanosheet based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires based on nanomold structure showed metallic conductance. The other wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

The DNA origami method provides a programmable bottom-up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nano-electronics and nano-photonics device fabrications. This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanomolds and nanosheets are used for the fabrication of nano-electronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanomolds and nanosheets create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanomold and nanosheet based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires based on nanomold structure showed metallic conductance . The other wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

The DNA origami method provides a programmable bottom up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nanoelectronics and nanophotonics device fabrications.
This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanoMOLDS are used for the fabrication of nanoelectronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanoMOLDS and create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanoMOLD based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires showed metallic conductance. The other two wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

Small DNA origami templates 90 nm x 70 nm DNA origami nanosheets with three functionalized sides holding a total of eight capture strands for decoration with gold nanoparticles were fabricated. Electroless gold growth is applied to selectively grow the gold nanoparticles until they merge into continuous nanowires. Finally, this work demonstrates the application of shape-controlled C-shaped gold wires as precisely tailored metal contacts to single, isolated nanowires to better understand the charge transport characteristics at different temperatures.

The DNA origami method provides a programmable bottom up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nano-electronics and nano-photonics device fabrications. This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanomolds1,2 and nanosheets are used for the fabrication of nano-electronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanomolds and nanosheets create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanomold and nanosheet based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires based on nanomold structure showed metallic conductance.1 The other wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

Small DNA origami templates 90 nm x 70 nm DNA origami nanosheets with three functionalized sides holding a total of eight capture strands for decoration with gold nanoparticles were fabricated. Electroless gold growth is applied to selectively grow the gold nanoparticles until they merge into continuous nanowires. Finally, this work demonstrates the application of shape-controlled C-shaped gold wires as precisely tailored metal contacts to single, isolated nanowires to better understand the charge transport characteristics at different temperatures.

The DNA origami method provides a programmable bottom up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nanoelectronics and nanophotonics device fabrications.
This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanoMOLDS are used for the fabrication of nanoelectronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanoMOLDS and create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanoMOLD based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires showed metallic conductance. The other two wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

The DNA origami method provides a programmable bottom up approach for creating nanostructures of any desired shape, which can be used as scaffolds for nano-electronics and nano-photonics device fabrications. This technique enables the precise positioning of metallic and semiconducting nanoparticles along the DNA nanostructures. In this study, DNA origami nanomolds1,2 and nanosheets are used for the fabrication of nano-electronic devices. To this end, electroless gold deposition is used to grow the AuNPs within the DNA origami nanomolds and nanosheets create eventually continues nanowires. In order to contact the fabricated nanostructues electrically, a method using electron-beam lithography was developed. The DNA origami nanomold and nanosheet based metallic wires were electrically characterized from room temperature down to 4.2K.
Temperature-dependent characterizations for four wires exhibiting different conductance at RT were performed in order to understand the dominant conductance mechanisms from RT to 4.2K. Two of these nanowires based on nanomold structure showed metallic conductance.1 The other wires deviated from pure metallic behavior and they showed thermionic, hopping and tunneling charge transport mechanism.

The fundamental mechanisms governing macroscopic freckle defect formation during directional solidification are studied experimentally in a Hele-Shaw cell for a low melting point Ga-25wt.%In alloy, and modelled numerically in 3D using a microscopic parallelised Cellular Automata lattice Boltzmann method. The size and distribution of freckles (long solute channels, or chimneys) is shown to be strongly dependent on the thermal profile of the casting, with flat, concave and convex isotherms being considered. For the flat isotherm case, no large-scale freckles form, while for concave or convex isotherms large freckles appear but in different locations. The freckle formation mechanism is as expected buoyancy-driven, but the chimney stability, its long-term endurance and its location, are shown to depend critically on the detailed convective transport through the inter-dendritic region. Flow is generated by curved isopleths of solute concentration. As solute density is different from that of the bulk fluid, gravity causes ‘uphill´ or ‘downhill’ lateral flow from the sample centre to the edges through the mush, feeding the freckle. An excellent agreement is obtained between the numerical model and real-time x-ray observations of a solidifying sample under strictly controlled temperature conditions.

Im ersten Teil dieses letzten Studienheftes wollen wir uns mit Reaktionen vertraut machen, bei denen aus einer prochiralen Verbindung selektiv chirale Verbindung gebildet wird, bei der ausschließlich eines der beiden Stereoisomere mit Chiralitätszentrum entsteht. Aus den Studienheften davor wissen wir schon, dass aus nichtchiralen Verbindungen mit prochiralem Zentrum meist Racemate entstehen. Faktoren, die zu einer Bevorzugung eines der beiden Stereoisomere führen, werden wir uns genau anschauen.
Im zweiten Teil wollen wir uns mit Retrosynthese und Syntheseplanung beschäftigen. Ausgehend von teils komplizierten Molekülen und Strukturen werden Sie sehen, wie durch eine gedankliche „Rückwärtsreaktion“ (Zerlegung in Bestandteile) ein Syntheseplan erstellt werden kann. Dazu wird das Zielmolekül immer weiter in seine Bestandteile, also hypotetische Ausgangsstoffe, zerlegt.

Elementorganische Verbindungen sind uns schon ganz am Anfang dieses Studiums seit dem ersten Studienheft über den Weg gelaufen. Bisher haben wir uns auf Substanzen beschränkt, die Hauptgruppenmetalle wie Magnesium, Natrium oder Lithium beinhalten. Denken Sie dabei zum Beispiel an die Aldol-Reaktion. Aber auch ein typisches Nebengruppenelement, nämlich das Zink, haben wir uns angeschaut.
Für Sie ist wichtig zu wissen, welche Bindungsverhältnisse in diesen metallorganischen Verbindungen vorherrschen. Das betrifft insbesondere die Umpolung der Bindung des Kohlenstoffs, wenn er an Metallen gebunden ist im Vergleich zur Bindung von elektronegativeren Elementen, wie den Halogenen, Stickstoff, Sauerstoff oder auch Schwefel. Damit soll klarwerden, dass dieses Kohlenstoffatom dann carbanionisch reagiert.

Das Ziel des ersten Teils dieses Studienheftes besteht darin, ein Gefühl beziehungsweise Verständnis von Nebenreaktionen zu bekommen, die beispielsweise bei nucleophilen Substitutionsreaktionen oder Additionen und Eliminierungen auftreten. Diese Nebenreaktionen sind meist Umlagerungen, haben teilweise ihren eigenen Mechanismus und führen vielfach zu unerwarteten Produkten, wie wir schon in der Vergangenheit sehen konnten. Wir werden uns intensiv damit beschäftigen, ob und wie diese Umlagerungen beeinflusst werden können und welche Varianten es gibt.
Des Weiteren werden wir schauen, welche weiteren Umlagerungen existieren und welche Produkte zu erwarten sind. Am Ende werden wir einen Blick auf elektrocyclische Reaktionen werfen und sehen, dass durch deren Übergangszustände und Zwischenstufen stereoselektiv Produkte gebildet werden.

Nachdem wir uns in der Organischen Chemie I in der Hauptsache mit Stoffklassen, funktionellen Gruppen und wichtigen Reaktionen beschäftigt haben und in der Organischen Chemie II die Reaktionsmechanismen genau beleuchteten, wollen wir uns im dritten Teil mit speziellen Themen der organischen Chemie beschäftigen. In diesem Studienheft wollen wir uns einzig und allein mit der Anordnung der Atome in Molekülen und den damit verbundenen Besonderheiten dieser Moleküle beschäftigen. Doch warum brauchen wir das ganze Wissen über den exakten Aufbau der Moleküle? Es ist speziell für die Pharmazie und Biochemie von grundlegender Bedeutung, genau zu wissen, wie Moleküle aufgebaut sind. Denn mit exakt der gleichen Summenformel, selbst mit gleicher Aneinanderreihung der Atome können unterschiedliche Wirkungen auftreten.
Deshalb werden wir noch einmal genau beleuchten, was Isomere sind und welche Arten es gibt. Dann werden wir uns die Auswirkungen anschauen, die vier unterschiedliche Substituenten an einem Kohlenstoffatom haben. Wichtig ist, dass Sie verstehen, dass unterschiedliche Stoffe oder Verbindungen da sind, wenn Sie die Stellung (Anordnung) der Substituenten im Molekül „vertauschen“. Zudem sollten Sie mit dem Begriff Stereoisomerie sicher umgehen können und wissen, was für Isomere da existieren und was das für Folgen auf die Reaktivität des Moleküls hat. Darauf aufbauend finden wir Moleküle, in denen mehr als ein Chiralitätszentrum existiert. Welche Auswirkungen das auf die Eigenschaften des Moleküls hat, werden wir am Schluss sehen.

The first evidence of azimuthal magnetorotaional instability was given some years ago by Seilmayer et al. (2014). A Taylor Couette Setup, filled with liquid metal, was exposed to magnetic field Bφ ~ r^ -1. The necessary current was supplied by a large frame of copper rods which caused a residual m=1 field disturbance. This imperfection caused a stationary dominant background flow. Since then, several changes took place to circumvent external asymmetries and influences. The main improvement was the symmetric current return path which eliminates the m=1 background flow and reduces stray fields. Now the AMRI wave is mainly located at the top of the cylinder, which is surprising since the theoretical prediction allows a symmetric wave with m=±1 configuration. However, the wave component from below is missing. Recent work indicate that thermal convection could be a possible source of symmetry breaking. We present experimental results which give evidence to the strong dependency on thermal boundary conditions which affect AMRI action in the volume.

Thallium (Tl) is a typical toxic metal, which poses a great threat to human health through drinking water and the food chain (biomagnification). China has rich Tl-bearing mineral resources, which have been extensively explored and utilized, leading to release of large amounts of Tl into the environment. However, research on Tl pollution and removal techniques is relatively limited, because Tl has not been listed within the scope of environmental monitoring in China for several decades. This paper reviewed Tl pollution in wastewater arising from various industries in China, as well as the latest available methods for treating Tl-containing industrial wastewater, in order to give an outlook on effective technologies for controlling Tl pollution. Conventional physical and chemical treatment technologies are efficient at removing trace amounts of Tl, but it proved to be difficult to achieve the stringent environmental standard (≤0.1–5 μg/L) cost-effectively. Adsorption by using newly developed nanomaterials, and metal oxide modified polymer materials and microbial fuel cells are highly promising and expected to become next-generation technologies for remediation of Tl pollution. With the potential for greater Tl contamination in the environment under accelerated growth of industrialization, researches based on lab-scale implementation of such promising treatment technologies should be further expanded to pilot and industrial scale, ensuring environmental protection and the safety of drinking water for sustainable development. Comprehensive insights into experiences of Tl pollution in China and in-depth perspectives on new frontier technologies of Tl removal from wastewaters will also benefit other nations/regions worldwide, which are susceptible to high exposure to Tl likewise.

Thallium (Tl) is an uncommon toxic element, with an even greater toxicity than that of As, Hg and Cd. Steel-making industry has been identified as an emerging new significant source of Tl contamination in China. This paper presents a pilot investigation of the contamination and geochemical transfer of Tl and associated metal(loid)s in river sediments affected by long-term waste discharge from the steel-making industry. The results uncovered an overall Tl contamination (1.96 ± 0.42 mg/kg) across a sediment profile of approximately 1.5 m in length, even 10 km downstream the steel plant. Highly elevated contents of Pb, Cu, Cd, Zn and Sb were found in the fluvial sediments, displaying strong positive correlations with Tl contents. Elevated levels of geochemically mobile Tl as well as Cd, Zn, Cu and Pb occurred in the fluvial sediments, signifying anthropogenic imprints from steel production activities at high temperature. Levels of contamination and ecological risk were calculated to be moderate to considerable for Tl, Cu, Zn and high to very high for Cd, Pb, Sb. The results highlight that there is a great challenge in view of potentially considerable Tl pollution due to continuous massive steel production in many other parts of China. It is high time to initiate process-based management of Tl contamination control for the ambient aquifer system in the steel-making area.

The grinding characteristic of a cassiterite-bearing skarn ore was investigated for the fine particle size range using an agitated ball mill. The applicability of Mineral Liberation Analyzer was investigated for the fine particle range. The appropriate liberation of cassiterite was determined with the help of tangible parameters such as the degree and coefficient of liberation and grade-recovery diagrams. The liberation of cassiterite was found to be in a satisfying range for downstream upgrading. A more etailed analysis of the liberation characteristics of the potential valuables together with a better understanding of the breakage characteristics of the gangue minerals will help to optimize the operation of the subsequent upgrading process. Therefore, the breakage behavior of the most important gangue minerals was analyzed. The effect of selectivity in breakage for the different minerals became visible.
A clear spreading for the mineral recovery versus size class indicated a mineral specific accumulation during milling. These trends lead to the assumption that the separation of the minerals into different particle size classes can be optimized by applying a specific energy input.

Image analysis data obtained from scanning electron microscopy provided data for a detailed evaluation of the separation efficiency for various processes involving the beneficiation of particulate materials. A dry magnetic separation by a drum type magnetic separator served as a case study to visualize effects of processing of a skarn ore with a high content of cassiterite as ore mineral (~4 wt%). For this material, iron oxides and silicates are the main gangue mineral groups. Based on the obtained data, partition curves were generated with the help of local regression.
From the partition curves, the separation efficiency was evaluated and the relevant particle properties deduced. A detailed analysis of the bias of the quantitative mineralogical data is presented. This bias was monitored and further analyzed in detail. Thorough analysis of feed and products of magnetic separation enabled identification of the most important factors that control losses of cassiterite to the magnetic product, namely the association with iron oxides and particle sizes below ~40 µm.
The introduced methodology is a general approach applicable for the optimization of different separation processes and is not limited to the presented case study.

Assessing the success of sensor-based sorting in the raw materials industry currently requires time-consuming and expensive empirical test work. In this contribution we illustrate the prospects of successful sensor selection based on data acquired by scanning electron microscopy-based image analysis. Quantitative mineralogical and textural data from more than 100 thin sections were taken to capture mineralogical and textural variability of two different ore types from the Hammerlein Sn-In-Zn deposit, Germany. Parameters such as mineral grain sizes distribution, modal mineralogy, mineral area and mineral density distribution were used to simulate the prospects of sensor-based sorting using different sensors. The results illustrate that the abundance of rock-forming chlorite and/or density anomalies may well be used as proxies for the abundance of cassiterite, the main ore mineral.
This suggests that sorting of the Hammerlein ore may well be achieved by either using a short-wavelength infrared detector - to quantify the abundance of chlorite - or a dual-energy X-ray transmission detector to determine the abundance of cassiterite. Empirical tests conducted using commercially available short-wave infrared and dual-energy X-ray transmission sensor systems are in excellent agreement with simulation-based predictions and confirm the potential of the novel approach introduced here.

A comprehensive quantitative mineralogical study on the Hämmerlein tin deposit in the Erzgebirge, Germany, not only yields insights into the genesis of Sn mineralization but also provides also important clues for beneficiation. The lithological units of the skarn and greisen deposit show significant differences in modal mineralogy and Sn deportment. These systematic differences are attributed to several stages of ore formation. Of greatest significance is a paragenetically late cassiterite-chlorite-fluorite-sulfide assemblage. This assemblage replaces pre-existing skarn lithologies and also forms stockwork mineralization in greisen-type ores developed at the expense of mica schist that surrounds the skarn. The co-genetic formation of the cassiterite-chlorite-fluorite-sulfide assemblage is captured by the mineral association parameter—a parameter that can be easily quantified from data acquired during automated mineralogy studies. To document the preferred mineral association, a ratio is introduced that illustrates how closely cassiterite—the only Sn mineral of economic relevance—is associated with chlorite, fluorite, and sulfides. This socalled MAMA ratio illustrates the strongly preferred association between cassiterite and chlorite. The results also illustrate that the abundance of rock-forming chlorite may be used as a proxy for the abundance of the much less common cassiterite. This proxy is well-suited to sort ore from poorly mineralized/unmineralized rock fragments early during the beneficiation process. Such separation may well be achieved by using a short wave infrared detector that is already deployed in commercially available sorting equipment. The case study illustrates the inherent link between the processes responsible for ore genesis, the definition of geometallurgical domains, and the selection of suitable beneficiation strategies.

Non-reciprocity of wave phenomena describes the situation where wave dispersion depends on the sign of the wave-vector, i.e., counter-propagating waves exhibit di↵erent wavelengths for the same frequency. Such behavior has been recently observed in heavy-metal/ferromagnetic interfaces with Dzyaloshinskii-Moriya coupling, and has also been known for coupled magnetic bilayers, where non-reciprocity is enhanced when the two layers are antiparallel aligned. Besides the conventional uses of spin-waves, non-reciprocity adds further functionalities, such as its potential applications in communications technologies and logical operations. In the current manuscript, we thus examine the spin-wave non-reciprocity induced by dipolar interactions in a coupled bilayer consisting of two ferromagnetic layers separated by a non-magnetic spacer. We derive an easy-to-use formula to estimate the frequency di↵erence provided by the non-reciprocity, which allows for choosing an optimal system in order to maximize the e↵ect. For small wave-numbers, non-reciprocity scales linearly, while for larger wave-vectors the non-reciprocity behaves non-monotonically, with a well-defined maximum. The study is carried out by means of analytical calculations that are complemented by micromagnetic simulations. Furthermore, we confirmed our model by experimental investigation of the spin-wave dispersion in a prototype antiparallel-coupled bilayer system. Since the relative magnetic orientation can be controlled through a bias field, the magnon non-reciprocity can be then turned on and o↵, which lends an important functionality to the coupled ferromagnetic bilayers.

Ziel dieser Masterarbeit war die Synthese der Steroidderivate 18-Oxocortisol (8a) und dessen deuteriertes Analogon 1,2-²H₂-18-Oxocortisol (8b). Die Darstellung erfolgte ausgehend vom strukturell ähnlichen Prednisolon (1). Dazu mussten zunächst orthogonale Schutzgruppen eingeführt werden, um selektiv Modifizierungen an der Steroidstruktur vornehmen zu können. Im Anschluss musste die 18-Methylgruppe funktionalisiert werden um die Einführung der Aldehydfunktion zu ermöglichen. Nach der darauffolgenden Entschützung sollte Derivat 7 erhalten werden, das sich von 8a und 8b lediglich in der C=C-Doppelbindung zwischen den Kohlenstoffatomen C-1 und C-2 unterschiedet und durch selektive Hydrierung oder Deuterierung dieser zu den Zielverbindungen umgesetzt werden kann.

The lecture gives an introduction to modern process analytical techniques in the industry and research.

The past years have seen a tremendous increase in computational power and hence a trend to employ more and more advanced numerical tools for the analysis of nuclear thermal hydraulics. Primary applications are accident analyses as well as safety assessment for new reactor systems and prominent directions are 3D computational multiphase fluid dynamics, coupled codes, and advanced BEPU analyses. While years ago it was believed that one day such tools may be able to replace experiments fully or in part, it is meanwhile commonly accepted, that a focus must be given on validation experiments for single effect problems and that such validation experiments should be preferably at original system t/h conditions to account for difficult upscaling conditions, and that such experiments need new instrumentation in order to get CFD grade data. The latter means field quantities of phase fraction, velocity and temperature at high spatial and temporal resolution.
The lecture gives an in-depth overview over novel field measuring techniques for nuclear thermal hydraulics experiments. We will briefly touch the field of distributed sensors for phase fraction, temperature and velocity and then dive into the field of advanced imaging techniques. We will discuss the application of well-known imaging techniques, such as high speed videometry, PIV and IR thermography and then come to computed tomography techniques, which are very useful to study multiphase problems. The methodological description of the basic physics and technology will be accompanied by application examples in nuclear safety research being pursued at the TOPFLOW facility at Helmholtz-Zentrum Dresden-Rossendorf.

The presentation gives a overview over recent activities in the field of tomographic imaging for multiphase flows.

The European Doctoral Training Network “Smart Tomographic Sensors for Advanced Industrial Process Control (TOMOCON)” gathers academic and industrial partners from different sectors with the mission to develop new fundamentals and technological solutions of advanced industrial control by tomographic sensors. It has received funding by the EU under the Marie Skłodowska-Curie scheme as an Innovative Training Network. It runs from September 2018 to August 2022 with 15 Early Stage Researchers, who are working as PhD students in 10 different European academic institutions. Within their research projects the doctoral students receive an extensive training in various fields of engineering and natural sciences being carried out in the frame of so called secondments at different industrial and academic partners as well as via three dedicated Summer Schools. The network is further supported by an Advisory Board with members from leading institutions in the field of process tomography.

Solid oxide electrolyzer cells pose a promising technology for the production of hydrogen gained from renewables, such as wind and PV. Due to the fluctuating nature of these sources, the transient behavior of SOEC under various load cases plays a crucial role in terms of their long-time stability, degradation behavior, conversion efficiency and application. This study presents a dynamic, 2D-FEM model of a single tubular SOEC. The transient operational behavior of the cell under fast load variations and different flow configurations is assessed based on the conducted simulations.

To evaluate the retention potential of concrete inside a nuclear waste repository for actinides under saline and hyperalkaline conditions, leaching experiments with actinide doped cementitious phases were performed in repository-relevant brines. Therefore, U(VI) and Cm(III) doped calcium silicate hydrate (C-S-H) phases with different calcium-to-silicon (C/S) ratios (1.0−2.0) were synthesized directly in presence of either U(VI) or Cm(III) and characterized by time-resolved laser-induced luminescence spectroscopy (TRLFS), infrared (IR) spectroscopy, powder X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM). The time-dependent release of Ca, Si, U or Cm from CSH phases into brines that contained either 2.5 M NaCl, 2.5 M NaCl/0.02 M Na₂;SO₄, 2.5 M NaCl/0.02 M NaHCO₃ or 0.02 M NaHCO₃ for U(VI) doped CSH phases or 2.5 M NaCl/0.02 M NaHCO₃ or 0.02 M NaHCO₃ for Cm(III) doped CSH phases was monitored in batch leaching experiments for 30 to 60 days. Subsequently, leaching induced changes of the C-S-H structure and of the U(VI) or Cm(III) coordination environment were investigated with TRLFS, IR spectroscopy and XRD. Results indicated that the U(VI) retention by C-S-H phases is maintained in the presence of NaCl rich solutions due to the formation of uranophane [1]. The presence of carbonate in saline leaching solutions increased the U(VI) mobility due to formation of Ca₂UO₂(CO₃)₃(aq) at moderate alkaline pH values [1]. Furthermore, an influence of the secondary CaCO₃ phases calcite, vaterite and aragonite was detected. Calcite contributed to the U(VI) retention which was shown with TRLFS [1]. The binding study of Cm(III) incorporated into C-S-H gel revealed at least two Cm(III) species: (i) Cm(III) substituted against Ca2+ from the C-S-H interlayer and (ii) Cm(III) incorporated in the polyhedral CaO plane of the C-S-H structure. Additionally, a luminescence line narrowing effect was observed indicating variations of the local surrounding of Cm(III) in C-S-H gel. Leaching experiments showed that Cm(III) is not mobilized by carbonate but becomes partially incorporated into secondary CaCO₃ phases. Recently, we started to investigate the Al and U(VI) incorporation into C-S-H phases at different Al/Si ratios (0.025−0.2) and synthesis temperatures (25°C or 200°C). The obtained phases were investigated with ² ⁷Al NMR, TRLFS, XRD and Raman microscopy. First results indicated an influence of the Al starting material and synthesis temperature on the Al incorporation.

Dy₂Ti₂O and Ho₂Ti₂O₇ have attracted enormous scientific interest because of the unusual spin-ice ground state and exotic excitations – magnetic monopoles. In this work, we investigated how the lattice reacted to the change of the monopole density from the spin-ice through the Kagome ice to the saturated monopole phase and whether the very slow monopole dynamics predicted in theory were also detectable in lattice effects. We have performed magnetostriction and thermal-expansion measurements with a capacitive dilatometer on Dy₂Ti₂O₇ at temperatures down to 0.28 K to explore the lattice effects in the different regimes: Indeed, we have observed a field-dependent lattice anomaly and have found lattice relaxation effects which could be related to previously proposed monopole dynamics. This research has been supported by the DFG within project C01 of SFB 1143.

We investigated the magnetic spin-1 perovskite Ba₃NiNb₂O₉ by means of complex ac susceptibility measurements at extreme sample conditions. Ba₃NiNb₂O₉ with cubic perovskite structure (Pm-3m) has a random occupation of Nb(66 %)/Ni(33 %) at the center of the cubic perovskite unit cell. Different from the isostoichiometric sister compound, Ba₃NiNb2O₉ with P-3m1 structure which shows both uud-spin configuration and multiferroicity, the magnetic properties of the investigated system have not been studied below 2 K yet. For our single crystals, we observe a spin freezing transition at around 0.7 K. Furthermore, the peak of 𝜒’ is suppressed by applying an external dc field of 200 mT and 𝜒” shows a sudden onset near the freezing temperature.

We present measurements of the thermal and the thermal-Hall conductivity as a function of temperature and magnetic field in the twodimensional dimer spin system SrCu₂(BO₃)₂. The thermal conductivity in zero magnetic field shows a pronounced peak around 4 K which is ascribed to a spin-gap opening. The low-temperature maximum is strongly suppressed by the application of magnetic field. This result implies that the majority of heat is conducted by phonons which interact with the magnetic excitations. Furthermore, a theoretical study predicted a strong thermal Hall signature due to anisotropies originating from the Dzyaloshinskii-Moriya interactions which lead to a topological character of triplon excitations [1]. Our detailed experimental investigation did not reveal such effect disproving the existence of topological transitions in the triplon band structure.

We report the observation of an anisotropic and inverted hysteresis loop in the antiferromagnetic all-in-all-out ordered phase of Nd₂Hf₂O₇ having a negative remnant magnetization. The hysteresis emerges once exceeding a characteristic magnetic-field strength 𝐻^⋆(𝑇) below the Neél temperature. The very unusual appearance of a negative remnant magnetization is observed for a field parallel to the [111] and [110] direction. However, for field parallel to [001] no hysteresis can be seen. For this orientation the projection of the field onto all four local spin directions is equal and, hence, both realizations of the all-in-all-out state gaining equal Zeeman energy through a canting of their spins. We show further, that the underlying all-in-all-out phase is established in Nd₂Hf₂O₇ for temperatures below 𝑇_𝑁 = 0.48 K and persists up to fields of 0.27 T. We account for the inverted hysteresis in terms of a theory of uncompensated domain-wall spins of spherical Domains forming inside a fully polarized single-domain state.

CrGe is a nonmagnetic transition-metal germanide with the B20 noncentrosymmetric cubic structure. In contrast, the isostructural MnGe and FeGe both show a helical spin order. We present dHvA-effect data on CrGe that were obtained employing capacitive torque Magnetometers in a 18 T/30 mK and a 33 T/340 mK system. In combination with our fplo calculations, we provide a detailed picture of the Fermisurface topology of CrGe. Furthermore, by comparing the calculated band structures of CrGe and MnGe, we discuss possible reasons for the absence of magnetic order in CrGe. Finally, our calculations indicate that substituting Ge by As or Sn will not lead to magnetic order.

The unavoidable existence of thermal hysteresis in these magnetocaloric materials is one of the central challenges limiting their implementation in cooling devices. Transforming the material in minor loops of the thermal hysteresis, however, allows achieving significant reversible effects even when the hysteresis is relatively large. In this work, we focus on the magnetocaloric properties of Heusler alloys under cycling. We compare thermometric measurements of the adiabatic temperature change in low magnetic fields and pulsed field experiments with calorimetric measurements of the isothermal entropy change when moving in minor hysteresis loops driven by magnetic fields [1, 2].

Non-centrosymmetric transition-metal mono-pnictides such as NbAs, NbP and TaAs attracted a lot of attention because their bandstructures show linear non-degenerate band crossings, dubbed Weyl nodes [1,2]. Additionally, for certain magnetic-field orientations, the highest de Haas-van Alphen frequencies observed are smaller than 50 T. For that reason, all bands are expected to be in the quantum limit at fields easily reachable by pulsed magnetic fields. Thus, these semimetals constitute an ideal playground to study the quantum limit by electric transport and magnetic-torque measurements. Our first results for NbP show an unexpected linear increase in magnetic-torque measurements. In our contribution we show the results of our magnetic-torque measurements on NbP, NbAs, TaP and TaAs in pulsed fields up to 70 T.

The metal-organic compound Cu(pz)₂(2-OHpy)₂, as well as high-field magnetometry. A low-temperature Minimum of the temperature-dependent local and uniform magnetizations at 𝑇_𝑚𝑖𝑛 indicates a presence of the magnetic order. Within the ordered state, a splitting of the ¹H NMR spectra reveals commensurate AF order, presumably of checkerboard type. The phase transition, manifested as a sharp maximum of the temperature-dependent ³¹P nuclear spin-lattice relaxation rate 1/𝑇₁, occurs at temperatures slightly lower than 𝑇_𝑚𝑖𝑛, indicating an easy-plane anisotropy as well as a crossover between isotropic and XY behavior.

We report on magnetic properties of a novel metal-organic S = 1 antiferromagnetic triangular spin compound with isolated Ni2+ triangles entitled as BHAP-Ni3. Specific heat measurements reflect an onset of magnetic correlation at low temperatures without any long-range order down to 300 mK, indicating the presence of an unusual magnetic ground state. ESR measurements performed at 1.5 K advocate this ground state to be a gapped one. Field-dependent magnetization measured on the single crystal shows anisotropic behavior with field applied parallel and perpendicular to the triangle plane. However, a clear plateau-like region is seen in both directions above 8 T which corresponds to half of the fully polarized value of Ni2+ moment. The presence of such half-magnetization plateau is quite unusual in the family of triangular magnets. High-field magnetization measurements using pulsed magnet show another field-induced plateau above 30 T corresponding to the fully polarized state of S = 1 triangles.

We present high-field electron spin resonance (ESR) studies of the honeycomb-lattice material 𝛼-RuCl3, a prime candidate to exhibit Kitaev physics. Two modes of antiferromagnetic resonance were detected in the zigzag ordered phase, with magnetic field applied in the 𝑎𝑏 plane. A very rich excitation spectrum was observed in the field-induced Quantum paramagnetic phase. The obtained data are compared with results of recent numerical calculations, strongly suggesting a very unconventional multiparticle character of the spin dynamics in 𝛼-RuCl₃. The frequency-field diagram of the lowest-energy ESR mode is found consistent with the behavior of the field-induced energy gap, revealed by thermodynamic measurements. This work was supported by DFG (project ZV 6/2-2).

In this work we report on the magnetocaloric effect of La2/3Ca1/3MnO3 (LCMO) and La2/3Ca1/3Mn0.94Cr0.06O3 (LCMCrO) manganite thin films grown by DC magnetron sputtering on LaAlO3 (100) substrates. X-ray diffraction shows that both doped and undoped films crystallize in the orthorhombic structure. Magnetic measurements show a decrease in both the Curie temperature, TC, and the saturation magnetization, MS, for the LCMCrO sample. The change in the magnetic entropy (deltaSm) was extracted from hysteresis loops at different temperatures around the ferromagnetic to paramagnetic transition, displaying a maximum of entropy change (deltaSm)max near TC in both films. Moreover, a shift in (deltaSm)max toward temperatures above TC with increasing magnetic field and a broadening of the entropy change curve were observed. Results of refrigeration cooling power show a lower efficiency for LCMCrO. In order to obtain a local insight into the magnetic interactions of these films, measurements of X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) were performed. XMCD suggests that an antiferromagnetic coupling between Mn4+ - Mn3+ is favored with Cr3+ incorporation, which reduces the Mn L2,3 XMCD signal and results in a decrease of MS and (deltaSm)max in LCMCrO films.

Thermal expansion, magnetostriction, and magnetization measurements under magnetic field and hydrostatic pressure were performed on a UAu₂Si₂ single crystal. They revealed a large anisotropy of magnetoelastic properties manifested by prominent length changes, leading to a collapse of the unit-cell volume accompanied by breaking the fourfold symmetry (similar to that in URu₂Si₂ in the hidden-order state) in the antiferromagnetic state as consequences of strong magnetoelastic coupling. The magnetostriction curves measured at higher temperatures confirm a bulk character of the 50K weak ferromagnetic phase. The large positive pressure change of the ordering temperature predicted from Ehrenfest relation contradicts the more than an order of magnitude smaller pressure dependence observed by the magnetization and specific heat measured under hydrostatic pressure. A comprehensive magnetic phase diagram of UAu₂Si₂ in magnetic field applied along the c axis is presented. The ground-state antiferromagnetic phase is suppressed by a field-induced metamagnetic transition that changes its character from second to first order at the tricritical point

Despite advances in prostate cancer therapy, dissemination and growth of metastases results in shortened survival. Here we examined the potential anti-cancer effect of the NF-B inhibitor parthenolide (PTL) and its water soluble analogue dimethylaminoparthenolide (DMAPT) on tumour progression and metastasis in the TRansgenic Adenocarcinoma of the Mouse Prostate (TRAMP) model of prostate cancer. Six-week-old male TRAMP mice received PTL (40mg/kg in 10% ethanol/saline), DMAPT (100mg/kg in sterile water), or vehicle controls by oral gavage thrice weekly until palpable tumour formation. DMAPT treatment slowed normal tumour development in TRAMP mice, extending the time-to-palpable prostate tumour by 20%. PTL did not slow overall tumour development, while the ethanol/saline vehicle used to administer PTL unexpectedly induced an aggressive metastatic tumour phenotype. Chronic ethanol/saline vehicle upregulated expression of NF-B, MMP2, integrin 1, collagen IV, and laminin, and induced vascular basement membrane degradation in primary prostate tumours, as well as increased metastatic spread to the lung and liver. All of these changes were largely prevented by co-administration with PTL. DMAPT (in water) reduced metastasis to below that of water-control. These data suggest that DMAPT has the potential to be used as a cancer preventive and anti-metastatic therapy for prostate cancer. Although low levels of ethanol consumption have not been shown to strongly correlate with prostate cancer epidemiology, these results would support a potential effect of chronic low dose ethanol on metastasis and the TRAMP model provides a useful system in which to further explore the mechanisms involved.

Extended dry storage of spent nuclear fuel is a relevant issue in many countries operating nuclear power plants. Beside regulatory and security aspects there are questions with respect to the long-term integrity of the spent fuel as this is of relevance for final transportation and reloading to final waste repository casks. Within the frame of the BMWi project DCS-MONITOR, we investigate the potentials of different methods for non-intrusive monitoring of dry cask storage containers with spent nuclear fuel. These are thermography, radiation-based methods, and acoustic methods. For all of them we study the sensitivity and cross-sensitivity with respect to defined changes in the nuclear fuel distribution inside the containers. The analyses are mainly based on numerical simulations but also include some dedicated experimental studies.

This invited talk about the effect of neutron flux on the microstructure of irradiated RPV steels was given to the participants of a Training School in the Framework of the European project SOTERIA.

Der Vortrag umfasst Aspekte der Herstellung, Mikrostruktur, Eigenschaften und Anwendung von pulvermetallurgisch hergestellten Werkstoffen. Als Beispielsysteme werden ODS-Fe-Cr-Legierungen, Verbundwerkstoffe für die Elektronikkühlung und Aluminiumverbundwerkstoffe betrachtet.

We studied the Cm(III) retention by calcium silicate hydrate (C-S-H), portlandite (Ca(OH)2) and their alteration products calcite, vaterite, and aragonite in high ionic strength carbonate-containing solutions representing specific formation waters. For this, we synthesized C-S-H gels with calcium to silicon (C/S) ratios of 1.0 and 2.0 in the absence and presence of Cm(III), resulting in Cm(III)-free and Cm(III) doped C-S-H gel, respectively. For phase identification purposes we applied X-ray diffraction (XRD) while for the identification of the Cm(III)/C-S-H binding mode we applied site-selective time-resolved laser-induced luminescence spectroscopy (TRLFS). The stability of Cm(III) doped phases under repository-relevant conditions was evaluated by studying the time-dependent release of Cm(III) from the Cm(III) doped C-S-H gel into leaching solutions containing 0.02 M NaHCO3 or 2.5 M NaCl/0.02 M NaHCO3 over 60 d. Speciation changes of Cm(III) due to leaching were followed with TRLFS while C-S-H structure alterations and secondary phase formation were monitored with XRD. From the results it could be concluded that Cm(III) is not mobilized by aqueous carbonate but either remains incorporated in the C-S-H structure and portlandite or becomes partially re-immobilized into secondary CaCO3 phases. The presence of NaCl led to an accelerated conversion of metastable secondary CaCO3 phases into calcite.

Sandwich packings consist of alternatingly stacked structured packing layers of different specific surface area. In such packings froth two-phase flow appears when the packing is operated between the loading limits of the layers. For this highly agitated flow regime, there is a lack of hydrodynamic data, in particular on gas-liquid interfacial area. Ultrafast X-ray tomography, a cross-sectional imaging technique with a frame rate of more than 1000 cross-sectional images per second, is applied to visualize the gas-liquid flow and to extract the gas-liquid interfacial area data via image post-processing methods. For that, we assessed different segmentation methods, that are, level set and gray level contour techniques.

Einleitung
Ungefähr 50% der Krebspatienten werden durch Strahlentherapie behandelt, und die Protonentherapie (PT) bietet hier aufgrund der begrenzten Eindringtiefe und des steilen Dosismaximums eine sehr gezielte Behandlungsform mit potentiell reduzierten Nebenwirkungen. Die Treffgenauigkeit der Protonentherapie kann jedoch durch Bewegungen und anatomische Veränderungen während der Therapie stark kompromittiert werden. Eine gleichzeitige Bildgebung mittels Echtzeit-Magnetresonanztomographie (MRT) wäre deshalb ideal. Bis heute existieren jedoch keine kombinierten Systeme für MRT und PT. Ziele dieser Studie waren die erste Integration eines MR-Scanners in eine PT-Strahlführung, die experimentelle Verifizierung der Ablenkung des Strahls und der Sekundärteilchen im Magnetfled des MRT-Scanners, die Überprüfung der Machbarkeit einer gleichzeitigen MR-Bildgebung und Bestrahlung, und die Kontrolle der MR-Bildqualität mit und ohne Strahleinfluss.

Material & Methoden
Ein offener MR-Scanner mit einem vertikalen Magnetfeld von 0.22 T (MRJ2200, Paramed Medical Systems SpA) wurde an einer strahldüsenlosen horizontalen Strahlführung (Ion Beam Applications SA) installiert, und durch einen kompakten Faraday-Käfig von Hochfrequenz-Interferenzen abgeschirmt (Abb. 1). Die Strahlablenkung und der Einfluss des Magnets auf die Sekundärteilchen im Strahl wurden mithilfe an einem PMMA-Phantom befestigter radiochromischer Filme (EBT3, Ashland) in einem 1 T Magneten gemessen und mit Monte-Carlo-simulationsbasierten Vorhersagen verglichen. Zur Überprüfung der MR-Bildgebung wurden anatomische MR-Bilder eines Probanden bei ausgeschalteter Strahlführung sowie MR-Bilder eines Gewebephantoms und eines dedizierten Bildqualitätsphantoms mit und ohne Strahleinfluss (bei 125 MeV und 5 nA) aufgenommen.

Ergebnisse
Die gemessene Ablenkung des Strahls sowie lokale Dosiserhöhung durch Sekundärteilchen im Magnetfeld waren gering (< 1 cm bzw. 2%) und zeigten sehr gute Übereinstimmung mit simulationsbasierten Vorhersagen. Die MR-Aufnahmen (Abb. 2) zeigten die für den verwendeten Scanner übliche Bildqualität. Es wurde keine Veränderung der Bildqualität durch die Strahlführungsmagneten und den Protonenstrahl beobachtet, jedoch eine gleichförmige, korrigierbare Bildverschiebung (< 1 mm) in Frequenzkodierrichtung.

Diskussion
Die Integration eines offenen MR-Scanners in den experimentellen Strahlengang einer Protonentherapie-Anlage war erfolgreich. Die Einflüsse des Magnetfelds des MRT-Scanners auf den Strahl sind vorhersagbar und eine gleichzeitige MR-Bildgebung und Bestrahlung ohne Bildverzerrung ist möglich. Dies rechtfertigt die Entwicklung eines ersten Prototyps für die MRT-integrierte Protonentherapie.

Background and purpose: Classical robust optimization considers uncertainties in patient setup and particle range. However, anatomical changes occurring during the treatment are neglected. Our aim was to compare classical robust optimization (cRO) with anatomical robust optimization (aRO), to quantify the influence of anatomical variations during the treatment course, and to assess the need of adaptation.
Materials and methods: Planning CT and weekly control CTs (cCTs) from 20 head and neck patients were analysed. Three intensity-modulated proton therapy (IMPT) plans were compared: conventional PTV-based plan; cRO, using solely the planning CT, and aRO, including additionally the first 2 cCTs in the optimization. Weekly and total cumulative doses, considering anatomical variations during the treatment, were calculated and compared with the nominal plans.
Results: Nominal plans fulfilled clinical specifications for target coverage (D98% ≥ 95% of prescribed dose). The PTV-based and cRO approaches were not sufficient to account for anatomical changes during the treatment in 10 and 5 patients, respectively, resulting in the need of plan adaptation. With the aRO approach, in all except one patient the target coverage was conserved, and no adaptations were necessary.
Conclusion: In 25% of the investigated cases, classical robust optimization is not sufficient to account for anatomical changes during the treatment. Adding additional information of random anatomical variations in the optimization improves plan robustness.

The main objective of the McSAFE project is the development of the Monte Carlo based multiphysics coupled methodologies for reactor analysis and safety investigations of different reactor systems. Key-research areas are e.g. advanced depletion methods, optimal coupling of MC-codes to thermalhydraulic solvers, time-dependent Monte Carlo and methods and algorithms for massively parallel simulations. The project has started in September 2017 under the coordination of KIT. Among the other partners are European research institutes and technical support organizations (VTT, JRC, CEA, HZDR, NRI, KTH,WOOD), electricity providers (CEZ, PreussenElektra) and consultants (DNC). The software developed within the project should allow for the high precision evaluation of core safety parameters and will be applicable also to VVER reactor types.

Objectives: The adenosine A2A receptor (A2AR) is a G-protein-coupled-receptor which is mainly expressed in the basal ganglia (including striatum) of the brain and in cells of the immune system. Radiotracers for A2AR imaging have emerged as promising candidates for the diagnosis of neurodegenerative and neurooncological diseases. Aiming at the development of such radiotracer with improved molecular imaging properties, a library of 21 fluorinated pyrazolo[2,3-d]pyrimidine derivatives was synthesized based on a recently published lead compound [1]. Among those, the highly affine 4 fluorobenzyl derivate 1 (Ki(hA2A) = 5.3 nM; Ki(hA1) = 220 nM) and the 2 fluorobenzyl derivate 2 (Ki(hA2A) = 2.1 nM; Ki(hA1) = 147 nM) were chosen for 18F isotopoic labelling although the introduction of 18F at non-activated aromatic positions is challenging. Herein, we report on the radiosyntheses of [18F]1 and [18F]2 via an alcohol-enhanced copper-mediated one-step radiofluorination and their first biological evaluation.

Methods: Three different labelling strategies for the synthesis of [18F]1 have been investigated (Fig. 1). The first two were using [18F]fluorobenzaldehyde ([18F]B) as intermediate, which was produced by nucleophilic radiofluorination of a trimethylammonium precursor of type A (step a). Compound [18F]B was used either in a reductive amination reaction (step b) or it was further reduced to the corresponding alcohol (step c) followed by an Appel bromination to get [18F]C (step d) which was finally used in a benzylation reaction (step e). The third strategy, a one-step approach, started from the boronic acid pinacol ester precursor of type D employing [18F]TBAF and Cu(OTf)2(py)4 in n-BuOH/DMA (step f). The specific binding of [18F]1 and [18F]2 was evaluated in vitro by autoradiography of mice brain slices using 1, 2 and ZM241385 as different blocking agents.

Results: The two- and four-step labelling strategies resulted in an overall radiochemical yield of only 1.4% and 10%, respectively for [18F]1 (non-isolated). Therefore, [18F]1 and [18F]2 were prepared by an alcohol-enhanced copper-mediated one-step radiolabelling approach starting from the corresponding boronic acid pinacol ester precursor D. Compound [18F]1 was obtained with a radiochemical yield of 52+7% (n = 5, EOB), a molar activity of 135+64 GBq/µmol (n = 4, EOS) and a radiochemical purity of >98%. Compound [18F]2 was synthesized with a radiochemical yield of 9+1% (n = 2, EOB), a molar activity of 132 GBq/µmol (n = 1, EOS) and a radiochemical purity of >98%. In vitro autoradiography performed with [18F]2 showed high binding in the striatum, which could be blocked by selective A2AR ligands thus proving the specificity of the new radiotracer (Fig. 1).

Conclusions: An efficient copper-mediated one-step radiolabelling procedure was established for two new highly affine A2AR radiotracers. In a first in vitro study on mice brain slices, [18F]2 demonstrated excellent imaging properties. Further biological in vitro and in vivo investigations are needed to completely evaluate the potential of both A2AR radiotracers.

Acknowledgments: This work has been supported by the the European Regional Development Fund and Sächsische Aufbaubank (project no. 100226753).

References: [1] Gillespie et al., Bioorg. Med. Chem. Lett. 2008, 18, 2924-2929.

In order to detect novel σ receptor ligands, the rigit spiro [[2]benzopyran-1,1'-cyclohexan]-4'-one was connected with amino moieties derived from σ₂ receptor preferring lead compounds resulting in mixtures of trans- and cis-configured amines 6, 18, and 27. In a four step synthesis the methyl acetals 6 were converted into fluoroethyl derivatives 13 and 30. The most promising σ₂ receptor ligand is the methyl acetal 6a bearing a 2,4-dimethylbenzylamino moiety. The fluoroethyl derivatives 13c and 13d reveal high σ₁ affinity but moderate selectivity over the σ₂ subtype. In mice 13c and 13d showed antiallodynic activity that is stronger than that of the reference σ₁ antagonist BD-1063 (34). Since the antiallodynic activity of 13c could only be partially reversed by the σ₁ agonist PRE-084 (35), it is postulated that a second mechanism contributes to its overall antiallodynic effect. In contrast, the antiallodynic effect of its diastereomer 13d can be totally explained by a σ₁ antagonism.

The 'serial' package as an extension to the programming language R enables reading and writing binary and ASCII data to RS232/RS422/RS485 or any other virtual serial interfaces of the computer.

The lithium-ion battery (LiB) market is growing rapidly which leads to a considerable increase of LiB wastes. Despite the enhancement in graphite consumptions, there is no graphite recycling process from LiBs so far. Thus, graphite usually remains in slags from the metallurgical treatments.
The LiB components contain cobalt (Co), lithium (Li) and graphite, counted as critical materials. The aim of the present thesis is to increase the recycling recovery of the LiBs by developing a new innovative process, which minimizes metal losses and is able to recover graphite. By using flotation two valuable products, one of graphite and one with the valuable metals, are recovered in the light of their integration to the value chain of LiB production.
Mineral liberation analysis (MLA), x-ray fluorescence (XRF) and x-ray diffraction (XRD) were used for characterization of the black mass to understand the liberation behavior of the crushed LiB particles. Flotation tests were carried out in an Outotec GTK Labcell, the main studied parameters are the pre-treatment with attritioning, the flotation pH and the reagents dosages. Kerosene was used as a promoter for graphite and MIBC as a frother.
It was found that graphite particles were fully liberated from the copper foils, and the organic layer on the active particles was removed which increases the separation efficiency. However, only 62 wt. % of the cathode active particles are liberated from the aluminum foil. Based on this characterization results, particularly the liberation degree, a new flowsheet is designed to concentrate all the active material (graphite, Co, Ni, Mn and Li) in the < 50 μm fraction without current foil particles. Flotation studies show that pretreatment, such as attritioning, improved the process efficiency while preserving the spherical shape of graphite. Graphite recovery is +98 % with a grade of 72 wt. % and the tailings recover more than 90% of the precious metals Co, Ni and Li from the spent LiBS, with the respective grades 27 wt. % Co, 7 wt. % and 2.5 wt. % Li. Most of the concentrate impurities are fine particles from cathode active materials, which could be removed with a desliming process and flotation cleaner stages. This research is at its beginning and is expected to bring about an innovative and useful process for the recycling industry, despite the challenges involved. This process can recover the graphite and the lithium, which are usually ending the slags. At present, there might be legitimate questions regarding the expense and benefits of graphite recycling. However, the treatment of LiBs will become necessary in the near future due to environmental issues as well as the scarcity and criticality of LiB components. Consequently, graphite will become a valuable and needed by-product from the metals recycling. The dependence on imports of graphite from China would be reduced, providing a solution to meet the significant predicted demand of battery grade graphite. Moreover, LiB as a key driver of the transition away from a carbon-based economy, it is necessary to ensure a truly positive impact over the lifecycle of LiB, and consequently to reach a closed-loop system.

The lithium-ion battery (LiB) market is growing rapidly. Consequently, LiB wastes will increase in the future and LiB components such as Co, Li, but also graphite, are forecast to be critical materials. These critical materials are contained in the black mass produced by LiBs recycling. This original research focuses on graphite beneficiation from cathode lithium metal oxides by flotation. Detailed characterization of the pyrolyzed black mass (inculding MLA, XRF and XRD) shows that the graphite particles are fully liberated from the copper foils, and the organic layer PVDF is removed. Batch flotation shows that pretreatment, such as attritioning, improves process efficiency while preserving the shape of spheriodized graphite. Concentrate impurities mainly comprise fine particles from cathode active materials, which can be removed with desliming and flotation cleaner stages. As an outlook, this reasearch is expected to bring about an innovative and useful process for the recycling industry.

The X2 VVER-1000 benchmark describes first 4 fuel cycles of the Khmelnitsky NPP 2nd unit with VVER-1000 reactor as well as some operational transients. The benchmark specifications contain description of the reactor core material, geometry and operational history supplemented by measured operational data and startup experiments. In this work, the hot zero power experiments conducted during the fresh core startup are modelled with the Serpent-2 Monte Carlo code. The numerical results are validated against the available measured core data. The calculated and measured values of a critical boron concentration, temperature reactivity effect, and control rod worth are in a very good agreement while the deviations lay within the measurement uncertainties. Since the power distribution was not measured at the hot zero power state, the obtained Serpent solution could be used as a reference for a deterministic codes verification.

Semiconducting nanowires (NWs) hold promises for functional nanoscale devices. Although several applications have been demonstrated in the areas of electronics, photonics and sensing, the doping of NWs remains challenging. Ion implantation is a standard doping method in top-down semiconductor industry, which offers precise control over the areal dose and depth profile as well as allows for the doping of all elements of the periodic table even beyond their equilibrium solid solubility. Yet its major disadvantage is the concurrent material damage. A subsequent annealing process is commonly used for the healing of implant damage and the electrical activation of dopants. This step, however, might lead to the out-diffusion of dopants and eventually the degradation of NWs because of the low thermal stability caused by the large surface–area-to-volume ratio.

In this work, we report on non-equilibrium processing (flash lamps) for controlled doping of drop-casted Si/SiO2 core/shell NWs with shallow- and deep-level dopants below and above their equilibrium solid solubility. The approach lies on the implantation of either shallow-level dopants, such as B and P, or deep-level dopants like Se followed by millisecond flash lamp annealing. In case of amorphization upon high-fluence implantation, recrystallization takes place via a bottom-up template-assisted solid phase epitaxy. Non-equilibrium Se concentrations lead to intermediate-band Si/SiO2 core/shell NWs that have room-temperature sub-band gap photoresponse when configured as a photoconductor device [1]. Alternatively, the formation of a cross-sectional p-n junction is demonstrated by co-implanting P and B in individual NWs at different depth along the NW core.
[1] Y. Berencén, et al. Adv. Mater. Interfaces 2018, 1800101

Bubble column reactors with exothermic reactions are often equipped with dense tube bundle heat exchangers. While there is some knowledge about the impact of such internals on hydrodynamics and mass transfer for narrow columns, its role in pilot-scale columns is less clear. In this paper we report on a study of hydrodynamics and mass transfer in a BCR of 4.2 m height and 0.392 m diameter. We investigated different tube arrangements with triangular and square pitch and tube diameters of 32×10-3 m and 45×10-3 m at the same cross-sectional coverage (~25%). The column was operated at homogeneous and heterogeneous flow conditions. A customized three-layer wire-mesh sensor was utilized to visualize gas phase dynamics and liquid mixing characteristics in the column’s cross-section. We found that sub-channel size is the most crucial geometric design parameter. Tracer mixing experiments reveal that internals enhance the liquid dispersion due to induction of large-scale liquid circulation. Mass transfer was studied with the oxygen stripping method. Here we found, that the effect of the internals on the gas-liquid mass transfer is almost negligible. Eventually, correlations for gas holdup, axial liquid dispersion and the volumetric gas-liquid mass transfer coefficient are given, which take the internals’ geometry into account.

In this talk I will introduce with a short view on the background of the transistor invention as a key element driving the topic of semiconductor doping. After that I will discuss examples of advanced doping including ion beam based and other methods: doping and alloying of germanium, hyperdoping of silicon, doping from deposited layers, doping of silicon nanowires, doping from deposited layers. In all cases the experiments were performed in correlation to nonequilibrium thermal processing using flash lamps in the millisecond time range.