Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

The bioavailability and toxicity of Zn in contaminated soils strongly depend on its speciation. Initially, Zn speciation is determined by the primary contaminants. Over time, primary phases dissolve and Zn may adsorb to various soil components and eventually become incorporated into newly forming mineral phases. The practical relevance of this process for the attenuation of Zn bioavailability depends on the time scale over which new mineral phases form and the thermodynamic stability of the newly formed phase.
In this study, a field soil (pH 6.4, 1.5% organic carbon, 15% clay) was contaminated with filter dust from a brass foundry containing 98% zincite (ZnO). We followed the dissolution and redistribution of Zn over 4 years using bulk and micro XAFS analysis.
Bulk XAFS shows that within 18 months, most zincite dissolved and Zn attached to various soil components, mainly as an outer sphere complex. Micro XAFS reveals both remnants of undissolved zincite as well as regions of Zn specifically adsorbed to Mn/Fe oxides and beginning formation of a Zn bearing solid phase (phyllosilicate or mixed layered hydroxide). After 36 months, we observe a second shell in the bulk XAFS spectrum (~2.1 Zn @ 3.11 Å; 1st shell 5.8 O @ 2.04 Å), further supporting the formation of a Zn bearing mineral. Micro XAFS data for the same time reveal tetrahedrally coordinated specifically adsorbed Zn in Mn rich zones, Zn attached to organic material as an outer sphere complex, and octahedrally coordinated Zn in large diffuse parts of the soil matrix with a spectrum similar to the bulk XAFS.
Our results show that in a near neutral soil, ZnO dissolved within one to two years. A short transient phase, during which Zn is predominantly bound as an outer sphere complex, was followed by specific Zn adsorption and the onset of the formation of a Zn mineral phase. These results demonstrate that within a few years, Zn may be redistributed and attenuated in a near neutral soil. In ongoing studies, we investigate the long term efficiency of this immobilization process, e.g., during soil acidification.

Uranium is present in the Earth’s crust at an average concentration of 2 mg/kg, similar to As and Mo, but ten times higher than Sb. It is enriched in granitic and phosphate rocks, lignite and monazite sands, and occurs in numerous minerals, uraninite (pitchblende), carnotite, and autunite being most abundant. During mining and ore processing (World production of U 35,000 Mg/a), these relatively insoluble, U(IV) and/or U(VI) containing minerals are converted into highly soluble and mobile U(VI) aqueous species, which may present an immediate risk for the environment, or are converted back to less mobile chemical forms. We will give an overview of processes, which influence the fate of U in this greatly perturbed biogeochemical cycle.
Even at low redox potential and in equilibrium with uraninite, the aqueous solution of soils, the vadose zone and aquifers is dominated by U(VI) species. The extremely complex speciation of U(VI) is influenced by pH, dissolved carbonate and the presence of organic ligands. The mobility of these species is reduced by sorption processes to minerals, insoluble natural organic matter, and biota. On the other hand, the presence of carbonate and organic ligands with strong affinity for uranyl may prevent sorption to surfaces and enhance the mobility. The migration of U is furthermore influenced by the formation of, or sorption to mobile colloids.
A strong immobilization of U presents the reduction to U(IV) and the subsequent precipitation as uraninite or other minerals. This process may proceed as a catalytic reaction on inorganic surfaces. Microorganisms, however, which are abundant even in U waste piles with high heavy metal concentrations, may be more important for U(IV) mineral precipitation. Processes involved are a direct biological reduction of U(VI) or an indirect reduction by changing redox potential and pH of the aqueous solution. Microorganisms can reduce the U mobility also by processes like bioaccumulation and biomineralization. Alternatively, particular groups of microorganisms can mobilize U from the ores by direct and indirect (metabolic-conducted) oxidation of U(IV), a process called bioleaching. Microorganisms can also increase the U mobility by releasing chelating ligands into the environment. Thus, they play one of the key roles in the biogeochemical cycling of U.

Antimony is used to harden the Pb cores of ammunition. Thus, between 4 and 10 tons of Sb are annually deposited on Swiss shooting ranges by bullets. Due to the relatively rapid weathering of the bullets, Sb is released into the soil, but little is known about its further fate. As part of investigations to determine the geochemical factors that control Sb mobility, we have determined the oxidation state and species of Sb in 6 shooting-range soils, using a combination of EXAFS (extended x-ray absorption fine structure) spectroscopy and ITFA (iterative transformation factor analysis), a technique particularly suited for quantitative speciation in complex matrices [1, 2].
Antimony concentrations varied between 1,000 and 17,000 mg/kg. In spite of a wide range of soil chemical conditions (pH, mineral and organic matter composition), we found only two Sb species. In the first species, Sb is surrounded by 6 O atoms at a distance of 1.97 Å, by 1 Fe atom at 3.09 Å, and by 2 Sb atoms at 3.33 Å. This arrangement suggests pentavalent Sb sorbed onto Fe or Mn oxides by forming a polynuclear inner-sphere sorption complex.
In the second species, Sb is surrounded by 2 O atoms at a distance of 1.98 Å, and by Sb atoms at 2.91 Å, 3.35 Å, 4.30 Å, and 4.52 Å. This structure is consistent with Sb(III) (hydr)oxide.
The (hydr)oxide species prevailed in a very acidic soil (pH 3.1), the sorption complex prevailed in a slightly acidic soil, and mixtures of both species occurred in calcareous soils (pH 7.5).
The results for Sb(V) are in agreement with previous findings suggesting that Sb is bound to Fe oxides. Antimony(III) solubility appears to be controlled by Sb(III) (hydr)oxide. Our results suggest that Sb remains tightly bound in soils, confirming our previous macroscopic observation that Sb is strongly enriched in the uppermost layer of a soil profile [3].

References
[1] Scheinost A. C., Rossberg A., Marcus M., Pfister S., and Kretzschmar R. (2003) Physica Scripta, in press.
[2] Rossberg A., Reich T., and Bernhard G. (2003) Analyt. Bioanalyt. Chem. 376, 631-638
[3] Knechtenhofer L. A., Xifra I. O., Scheinost A. C., Flühler H., Kretzschmar R. (2003) J. Plant Nutr. Soil Sci. 166, 84-92.

wird nachgereicht

wird nachgereicht

Kolloide sind Bestandteile aller aquatischen Systeme. Das Verhalten der Kolloide in der Umwelt, deren Mobilisierung, Transport und Abscheidung und somit auch die Relevanz sind noch nicht vollständig verstanden. Dies liegt zum Teil an der Tatsache, dass die Kolloidanalytik extrem aufwändig ist. Sie gehört nicht zur Standardanalytik eines Wasserlabors. Keine Technik ist bisher zufriedenstellend in der Lage, Kolloide in ihrem gesamten Größenbereich auch bei geringsten Konzentrationen gleichzeitig zu quantifizieren und zu identifizieren. In der Regel ist eine Kombination von verschiedenen Techniken notwendig, um ausreichend Informationen über das Verhalten der Kolloide zu erhalten. Für die Bestimmung der Oberflächeneigenschaften stehen kaum Methoden zur Verfügung. Eine weitere, nicht zu unterschätzende Schwierigkeit ist die Probennahme und Probenaufbereitung. Für die Untersuchung von Kolloiden sind spezielle Probennahmetechniken und Protokolle notwendig, da ansonsten die ungestörten, natürlichen Bedingungen durch (Probennahme-)Artefakte maskiert werden. Dieser Artikel soll in Form einer Übersichtsarbeit Hinweise zur Probennahme geben und die verschiedenen Möglichkeiten der Kolloidanalytik aufzeigen.

Kolloide sind Bestandteile aller aquatischen Systeme. Sie umfassen Feststoffe, deren Größe in zumindest einer Dimension zwischen 1 und 1.000 nm liegt. Sie können anorganischer (z. B. Tonteilchen, Karbonate oder Silikate) oder organischer (z. B. Ruß oder höhermolekulare organische Verbindungen wie Huminstoffe) Natur sein. Auch Bakterien, Viren, Sporen und Algen in diesem Größenbereich können zu den Kolloiden gerechnet werden (häufig als Bio-Kolloide bezeichnet). Kolloide können den Transport von (Schad-)stoffen im Untergrund und in Oberflächengewässern beeinflussen, insbesondere von Spurenelementen und hydrophoben organischen Verbindungen, oder zu unerwünschten Effekten wie Porenraumreduktion (Clogging) führen. Für die Hygiene des Trinkwassers ist das Verhalten von Bakterien, Viren und Sporen (den Bio-Kolloiden) von besonderer Bedeutung. Bisher ist das Verhalten von Kolloiden nur unzureichend verstanden. Dieser Artikel soll einen Beitrag zu dem Verständnis des physikalischen Verhaltens der Kolloide, deren Vorkommen in der aquatischen Umwelt sowie Relevanz in Form einer Übersichtsarbeit leisten.

Different reconstruction techniques are used to reconstruct the distribution of the physical characteristics, describing a sample under investigation, from a set of tomographic projections. We present a technique for the evaluation of the reconstruction quality. The technique is based on the comparison of two images (phantom and reconstructed image) by means of the correlation coefficient and of the mean square error between them. In parallel, the correlation coefficient and mean square error are calculated for the wavelet transforms of the phantom and reconstructed images. The scales for the wavelet transform are chosen in agreement with the major geometric parameters of the phantom. Then the correlation coefficient of the wavelet transform with the chosen scale yields an evaluation of the quality of the phantom parameters reconstruction. The accuracy of the parameters reconstruction is determined by the mean square error for the selected scale. The phantom used for the analysis is a medium with randomly distributed grains. The distribution is characterized by two parameters: grain size and grain density (average number of grains per unit area). The parameters are used as the scales for the wavelet transform calculation. We make a comparison of the Algebraic Reconstruction Technique (ART) and the Filtered Back Projection Algorithm.

Kolloide in Bergwerkswässern

wird nachgereicht

Beitrag zu "Forschung für Mensch und Umwelt. Jahresbericht 2003 des FZR"

The magnetic anisotropy in amorphous soft magnetic FeCoSiB films is modified by He-ion irradiation. A realignment of uniaxial anisotropy depending on the applied field direction in the irradiated areas is observed by magnetometry and complementary domain observation by Kerr microscopy. Using irradiation together with photolithography the films were treated locally, resulting in ‘anisotropy patterned’ structures. Complicated periodic domain patterns form due to the confined anisotropy distribution. Overall magnetic properties and domain patterns can be adjusted.

Driven by the requirement of high cutting efficiency and improvement of wafer flatness wire sawing of GaAs single crystals under brittle material removal conditions has been studied. Crack nucleation and crack propagation were investigated by indentation and scratching tests on polished {100}-oriented semi-insulating GaAs wafers. Based on these results a concept has been developed to control the force balance in the cutting slits so that the deflection of the wires perpendicular to the cutting planes is minimal resulting in cuts of high flatness. The concept has been successfully introduced in mass production of GaAs wafers.

Systematic Slow Positron Implantation Spectroscopy (SPIS) and Atomic Force Microscopy (AFM) studies of various 6H-SiC samples are presented to clear the role of conductivity type, crystal quality, ion implantation (B+, Al+, N+), and annealing (1.650 °C) on the formation of continuous long furrows (undulations) running in one direction across the wafer surface. It is found that the observed changes in surface morphology are primary the result of thermal activation and thus occur independent of conductivity type, crystal quality, and type of ion implantation. In terraces in-between the long furrows, stripe like islands with a discrete height in the nanometer range have been observed which may have some link with the ion implantation chosen. SPIS results clearly indicate the formation of vacancy clusters in n-type material which are connected with the mobility of nitrogen in the samples at elevated temperatures. It is found that defect profiling by SPIS is not influenced by the changes in surface morphology observed due to annealing.

In verfahrenstechnischen Anlagen der Flüssig-Flüssig-Stoffübertragung kommt es an der Phasengrenze zwischen den nicht mischbaren Flüssigphasen häufig zur Ausbildung hydrodynamischer Instabilitäten. Sie sind mit komplexen Geschwindigkeitsfeldern in den Flüssigphasen, insbesondere in den grenzschichtnahen Regionen verbunden und führen zu einem starken Anstieg der pro Zeiteinheit übertragenen Stoffmenge. Die Lösung der Diffusionsgleichung reicht in diesem Fall zur Vorausberechnung des für Auslegungszwecke bedeutsamen Stoffdurchgangskoeffizienten nicht mehr aus. Chemische Reaktionen stellen Quellen oder Senken von Wärme und Stoff dar, die das Auftreten von Instabilitäten begünstigen und die mathematische Beschreibung zusätzlich erschweren.

Im Rahmen der vorliegenden Arbeit wurden experimentelle und numerische Untersuchungen zum Flüssig-Flüssig-Stoffübergang in einem vertikalen Kapillarspalt durchgeführt. Reaktionsfreie Stoffübergänge und solche mit einer exothermen chemischen Reaktion an der Phasengrenze zeigten eine große Vielfalt von Konvektionsstrukturen, wie Rollzellen, Thermiken und das doppeldiffusive Fingerregime. Die Visualisierung der Transportvorgänge erfolgte durch das Schattenschlierenverfahren. Die Beobachtungen wurden hinsichtlich geometrischer Eigenschaften von Konvektionsstrukturen sowie deren zeitlicher Änderung ausgewertet. Dazu zählten insbesondere das Längenwachstum von Thermiken und horizontale Wellenlängen von Fingerstrukturen.

Zur mathematischen Beschreibung der Phänomene im Kapillarspalt wurde ein Modell entwickelt, welches auf den gekoppelten, zweidimensionalen Transportgleichungen von Impuls, Wärme und Stoff beruht. Es berücksichtigt dichte- und grenzflächenspannungsgetriebene Instabilitätsmechanismen sowie die besonderen Durchströmungseigenschaften des Kapillarspalts. Die Phasengrenze wurde als eben angenommen. Die Lösung der Modellgleichungen erfolgt auf numerischem Wege durch ein Computerprogramm.

Das Modell ist in der Lage, die beobachteten Instabilitätsphänomene qualitativ richtig wiederzugeben. Mit Hilfe von Simulationsrechnungen konnte der Mechanismus aufgeklärt werden, der zum schnelleren Rückgang des Stoffdurchgangskoeffizienten im Rollzellenregime der rein grenzflächenspannungsgetrieben Instabilität im Vergleich zum Vorgang mit überlagerter Dichtekonvektion führt. Des Weiteren gelang der Nachweis des doppeldiffusiven Fingerregimes beim Stoffübergang mit exothermer Grenzflächenreaktion. Die berechnete Erhöhung des Stoffdurchgangskoeffizienten stimmt mit Angaben in experimentellen Arbeiten anderer Autoren überein.

Different ways of generation of THz radiation are reviewed and our scalable emitter for intense pulsed THz radiation is presented. In the second part of the talk issues ralated to Bloch gain such as the fundamental understanding of the role of scattering processes and the role of electric field domains are adressed. Our approach to search for Bloch gain is discussed.

Dynamics of the Molten Salt Reactor - one of the 'Generation IV' concepts - was studied in this paper. The graphite-moderated channel type MSR was selected for the numerical simulation of the reactor with liquid fuel. The MSR dynamics is very specific because the fuel flow influences the delayed neutrons distribution. Presently, there are not many accessible numerical codes appropriate for the MSR simulation, therefore the DYN3D-MSR code was developed based on the FZR in-house code DYN3D. It allows calculating of full 3D transient neutronics in combination with parallel channel type thermal-hydraulics. By means of DYN3D-MSR, several transients typical for the liquid fuel system were analyzed. Those transients were initiated by reactivity insertion, by overcooling of fuel at the core inlet, by the fuel pump start-up or coast-down, or by the blockage of selected fuel channels. The results of these transient studies have shown that the dynamic behavior of MSR is acceptable with respect to the reactor safety.

Plasma Immersion Ion Implantation Under Industrially Relevant Conditions

Plant-measured data provided within the specification of the OECD/NEA VVER-1000 coolant transient benchmark (V1000CT) were used to validate the DYN3D/RELAP5 and DYN3D/ATHLET coupled code systems. Phase 1 of the benchmark (V1000CT-1) refers to the MCP (main coolant pump) switching on experiment conducted in the frame of the plant-commissioning activities at the Kozloduy NPP Unit 6 in Bulgaria. The experiment was started at the beginning of cycle (BOC) with average core expose of 30.7 effective full power days (EFPD), when the reactor power was at 27.5% of the nominal level and 3 of 4 MCPs were operating. The transient is characterized by a rapid increase in the primary coolant flow through the core and, as a consequence, a decrease of the space-dependent core inlet temperature. Control rods were not changing their positions during the transient. Both DYN3D/RELAP5 and DYN3D/ATHLET analyses were based on the same reactor model, including identical MCP characteristics, boundary conditions, benchmark-specified nuclear data library and nearly identical nodalization schemes. In addition to validation of the coupled code systems against measured data, a code-to-code comparison between simulation results has been performed to evaluate relevant thermohydraulic models of the system codes RELAP5 and ATHLET.

A comprehensive study on the migration of di- and tri-interstitials in silicon is performed using classical molecular dynamics simulations with the Stillinger-Weber potential. At first the structure and energetics of the di- and the tri-interstitial are investigated, and the accuracy of the interatomic potential is tested by comparing the results with literature data obtained by tight-binding and density-functional-theory calculations. Then the migration is investigated for temperatures between 800 and 1600 K. Very long simulation times, large computational cells and different initial conditions are considered. The defect diffusivity, the self-diffusion coefficient per defect and the corresponding effective migration barriers are calculated. Compared to the mono-interstitial, the di-interstitial migrates faster, whereas the tri-interstitial diffuses slower. The mobility of the di- and the mono-interstitial is higher than the mobility of the lattice atoms during the diffusion of these defects. On the other hand, the tri-interstitial mobility is lower than the corresponding atomic mobility. The migration mechanism of the di-interstitial shows a pronounced dependence on the temperature. At low temperature a high mobility on zigzag-like lines along a <110> axis within a {110} plane is found, whereas the change between equivalent <110> directions or equivalent {110} planes occurs seldom and requires a long time. At high temperature a frequent change between equivalent <110> directions or {110} planes is observed. During the diffusion within {110} planes the di-interstitial moves like a wave packet so that the atomic mobility is lower than that of the defect. On the other hand, the change between equivalent {110} migration planes is characterized by frequent atomic rearrangements. The visual analysis of the tri-interstitial diffusion reveals complex migration mechanisms and a high atomic mobility. The diffusivities and effective migration barriers obtained are compared with the few data from the literature. The implications of the present results for the explanation of experimental data on defect evolution and migration are discussed.

The deposition of suitable hard protective coatings onto organic substrates for ophthalmic applications faces several challenges, such as proper surface preparation to ensure the adhesion to the rigid substrate and a delicate balance between hardness and flexibility. In this work it is shown that SiOxCy :H-based protective coatings grown by plasma enhanced chemical vapor deposition (PECVD) from mixtures of hexamethyldisiloxane and oxygen, can be used as protective buffer coatings between the soft and easily scratchable substrate and the antireflection stack that might be applied on top of it. These coatings must show absence of optical absorption and require index matching with the substrate. To meet these conditions, a three-phase multifunctional coating PECVD deposition method has been developed, in which a progressive decrease towards the surface in the carbon content of the SiOxCy:H hard coat has been implemented. Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy characterization of the individual layers that compose the multilayer functional structure has been performed. The comparison of the results obtained from each spectroscopy shows the complementarity of these techniques and allows optimizing the protective coating performance from the optical and mechanical points of view.

The performance and in-beam imaging capabilities of two position-sensitive gamma-ray detectors consisting of Hamamatsu avalanche photodiode arrays (S8550) individually coupled to crystals of cerium-doped lutetium oxyorthosilicate (LSO) are presented. The two detectors were operated in coincidence at the medical beam line of the Gesellschaft für Schwerionenforschung, in Darmstadt, Germany. In a first set of experiments, their imaging performance was tested before, during, and after the irradiation of phantoms of polymethylmethacrylate with carbon ion beams with fluences equivalent to 1000 typical daily therapeutic fractions. Only minor energy, time, and spatial resolution deterioration was observed, with the initial values being recovered after stopping the irradiation. A second set of experiments successfully imaged the depth distribution of positron emitter radionuclides created in a phantom that stopped the high-energy carbon ion beam. The particular details for the in-beam PET acquisition are shortly outlined. The obtained results show that LSO is a suitable material for in-beam PET and that its coupling with avalanche photodiode arrays is feasible for a PET system dedicated to in-beam monitoring of ion therapy.

Aim of this work was, to investigate the preparation of Si NC memories by sputter deposition. The milestones are as follows:

• Review of relevant literature.
• Development of processes for an ultrathin tunnel-oxide and high quality sputtered SiO2 for use as control-oxide.
• Evaluation of methods for the preparation of an oxygen-deficient silicon oxide inter-layer (the precursor of the Si NC layer).
• Characterization of deposited films.
• Establishment of techniques capable of probing the phase separation of SiOx and the formation of Si NC.
• Establishment of annealing conditions compatible with the requirements of current CMOS technology based on experimental results and simulations of Si NC formation.
• Preparation Si NC memory capacitors using the developed processes.
• Characterization of these devices by suitable techniques. Demonstration of their memory functionality.

The coolant mixing in the downcomer and the lower plenum of pressurized water reactors (PWR) is significant for safety assessment of boron dilution and cold water transients.

The research project FLOMIX-R within the 5th Framework Programme of EC had the objective to obtain experimental data on the relevant coolant mixing phenomena using improved measurement techniques with enhanced resolution in space and time for CFD validation.

Recent experiments at the Rossendorf test facility ROCOM were integrated into this research project. ROCOM is a 1:5 scaled Plexiglas model of a German PWR allowing conductivity measurements by wire mesh sensors for analyzing the mixing pattern at selected positions in the reactor pressure vessel and velocity measurements by LDA technique.

A few benchmark problems based on selected experiments were used to study the effect of different turbulent mixing models under various flow conditions, to investigate the influence of the geometry, the boundary conditions, the grid and the time step in the CFD analyses. In doing the calculations the Best Practice Guidelines for nuclear reactor safety calculations have been followed. Results of this numerical mixing studies will be discussed.

The coolant mixing is of relevance for two classes of accident scenarios – boron dilution and cold-water transients. Experimental investigations and numerical simulations of coolant mixing in the downcomer and the lower plenum of PWRs was the topic of the EU-Project “FLOMIX-R”. The results of the project showed, that coolant mixing has a high relevance for nuclear safety. The coolant mixing is the only inherent mechanism, which reduces risks of power excursions. For the investigation of the relevant mixing phenomena, the Rossendorf test facility ROCOM has been used. ROCOM is a 1:5 scaled Plexiglas model of the PWR Konvoi allowing conductivity measurements by wire mesh sensors and velocity measurements by the LDA technique. Series of experiments were performed at ROCOM to study the mixing of a slug of lower borated water during the start-up of the first main circulation pump.

The CFD calculations were carried out with the code CFX-5. A complex hybrid mesh with the size of 2 million nodes and 4 million elements was used. The turbulence was modeled with the SST model.

Due to the strong momentum insertion during the pump start-up, a dominating horizontal component of the flow was observed near the inlet nozzle leading to a circumferential flow around the core barrel. Therefore, the injected slug is distributed into two main jets, and the maximum of the tracer concentration at the core inlet appears firstly at the location opposite to the loop where the tracer was injected. For turbulent flows the CFD-Code CFX-5 was validated for turbulent, momentum driven mixing. A better description of the mixing processes inside the RPV is the basis of a more realistic safety assessment concerning boron dilution scenarios.

The influence of density differences between the primary loop inventory and the Emergency Core Cooling water on the mixing in the downcomer of a Pressurised Water Reactor (PWR) was analyzed at the Rossendorf coolant mixing test facility ROCOM. ROCOM is 1:5 scaled model of a German PWR designed for experimental coolant mixing studies. It is equipped with advanced instrumentation, which delivers high-resolution information characterizing either temperature or boron concentration fields. A series of experiments was performed on mixing under the influence of density differences. Water with higher density was injected into the cold leg of the reactor model. Wire mesh sensors measuring the concentration distribution of a tracer added to the injected water were installed in the upper and the lower part of the downcomer. The data were used for CFD code validation. An experiment with 5% of nominal, constant flow rate in one loop (magnitude of natural circulation) and 10% density difference between ECC and loop water was selected for validation of the CFX-5 code. The turbulence was modeled with the BSL Reynolds stress turbulence model and a mesh with two million control volumes was used.

The results of the experiment as well as of the numerical calculations show, that buoyancy effects dominate the mixing. While at higher mass flow rates (close to nominal conditions) the injected slug propagates mainly in circumferential direction around the core barrel, the buoyancy effect partly suppresses this circumferential propagation. The ECC water falls down in an almost straight streamline and reaches the lower downcomer sensor position directly below the affected inlet nozzle. Therefore, the density effects play an important role during natural convection with ECC injection in PWRs. It was important to point out, that CFX-5 is able to cope the specific flow pattern and mixing phenomena.

In preparation for thermochromatographic adsorption studies of Lr in metal columns at temperatures up to 2000 K we investigated the metal adsorption of Cm and Bk. Cm was chosen to model Lr as a trivalent metal and Bk as a trivalent actinide having a (divalent) fn+1s2 ground state configuration. 250Bk electroplated on tantalum and 248Bk/246Cm implanted in zirconium foils were used as actinide sources. To carry out an adsorption experiment the actinide sources were placed at the starting position of the thermochromatographic columns and hold for 30 min at 1850 K. Standard enthalpies of adsorption were calculated from the experimental results and compared with calculations using a semi-empirical method. Based on these results, the capability of the method for studying electronic and metallic state properties of the heaviest actinides up to Lr is discussed.

For the investigation of air/water slug flow, a horizontal channel with rectangular cross-section was build at Forschungszentrum Rossendorf. The channel allows the investigation of air/water co- and counter current flows under atmospheric pressure, especially the slug behaviour. Optical measurements were performed with a high-speed camera, and were complemented by simultaneous dynamical pressure measurements.

CFD simulation of the stratified co-current flow was performed using the code CFX-5 applying the two fluid model with the free surface option. The grid contains 400000 control volumes. The tubulence was modeled separately for each phase using the k, w-turbulence model. The results show wave formation up to slug development with closure of the whole channel cross section, where the slug is propagating towards the outlet of the channel with an increasing speed compared to the water velocity and an increase of the pressure level in the channel after the slug front.

The qualitative slug formation in the CFX calculation is in good agreement with the experiment, while the calculated pressure distribution shows higher peak values than the measured one.

A data set of five transients at different VVER type nuclear power plants was collected in order to validate neutron kinetics/thermal hydraulics codes. Two of these transients ‘drop of control rod at nominal power at Bohunice-3’ of VVER-440 type and ‘coast-down of 1 from 3 working MCPs at Kozloduy-6’ of VVER-1000 type, were then utilised for code validation. Eight institutes contributed to the validation with 10 calculations using 5 different combinations of coupled codes. The thermal hydraulic codes were ATHLET, SMABRE and RELAP5 and the neutron kinetic codes DYN3D, HEXTRAN, KIKO3D and BIPR8. The general behaviour of both the transients was quite well calculated with all the codes. Even an elementary modelling of coolant mixing in reactor pressure vessel under asymmetric transients improved correspondence to the measurements. Some differences between the calculations seem to indicate that fuel modelling and treatment of VVER-440 control rods need further consideration. The simultaneous validation interacted with the data collection effort and thus improved its quality. The complexity of data collection systems and sometimes conflicting data, however, called for compromises and interpretation guides that also taught the analysts balanced plant modelling.

The development of coupled codes, combining thermal-hydraulic system codes and 3D neutron kinetics codes, is an important step to perform best-estimate calculations for plant transients of nuclear power plants. For applications in safety analysis, these coupled codes should be validated by benchmark calculations and, preferably, by comparison with plant transient data from operating plants. In addition, the results should be supplemented by applying uncertainty and sensitivity analysis methods, which allow to identify relevant parameters of models and solution procedures affecting the results and to quantify their relative importance. Both objectives were part of the VALCO project. The aspect of validation is presented in [S. Mittag, et al., 2004. Neutron-Kinetic Code Validation against Measurements in the Moscow V-1000 Zero-Power Facility, in press; T. Vanttola et al., 2004. Validation of coupled codes using VVER plant measurements, in press], the aspect of a comprehensive uncertainty and sensitivity analysis for coupled code calculations is the topic of this contribution. The results and experiences obtained by the analysis for two plant transients in a VVER-440 and a VVER-1000, respectively, are presented and discussed.

Uranium is of great importance for the Morsleben radioactive waste disposal site. Its retention by both backfilling materials and the overlying rock was determined in batch sorption experiments over a period of 400 days. There, the solution simulated the brines typical for this site. The observed retention at the backfilling and overlying rock materials was in the regions of 95.8 to 100% and 92.7 to 98.1%, respectively. The solubility of solid U₃O₈ in these brines was determined to be between 5*10^-9 and 9*10^-6 mol/L uranium.

The project was supported by the BfS under the contract No.: 9M 212230-62

The time dependence of the reduction of Np(V) to Np(IV) by various natural and synthetic humic substances was studied under anaerobic conditions between pH 3.5 and pH 9. For Np speciation in solution liquid-liquid extraction, NIR absorption spectroscopy, laser-induced photoacoustic spectroscopy (LIPAS) and ultrafiltration were applied. In comparison to natural humic substances, synthetic humic acids lead to a stronger reduction of Np(V) to Np(IV). The Np(IV) formed in the course of the experiments is stabilized in form of Np(IV) humate complexes, whereas the remaining Np(V) occurs as NpO2+ ion or Np(V) humate depending on pH. The higher reduction potential of the synthetic humic acids can be attributed to their higher phenolic/acidic OH group contents compared to natural humic substances. The influence of phenolic/acidic OH groups on the redox behavior of humic substances was verified applying a synthetic humic acid with blocked phenolic/acidic OH groups.

Uranium plays an important role in the long term safety assessment of nuclear waste repositories. It is therefore necessary to determine its correct thermodynamic data. However, the solubility of tetravalent uranium is not easily to measure because it shows a strong tendency to hydrolyse and to form hydroxides and hydrous oxides of low solubilities. Reported solubility products of U(IV) species are often too high due to the neglection of colloidal particles. Laser-induced breakdown detection (LIBD) provides an opportunity to detect such colloids down to a size of some nanometres at concentrations in the ppt range.
Solutions of U(VI)/HClO4/NaClO4 were reduced in an electrochemical cell under inert gas. The resulting U(IV) solutions were titrated coulometrically. Samples of the solution were pumped into a cuvette and investigated for the presence of colloids by LIBD. The pH of the onset of colloid formation and the U(IV) concentration were used to determine the solubility product of uranium(IV) hydroxide.

The synthesis of 1-(5-chloro-2-{2-[(2R)-4-(4-[¹⁸F]fluorobenzyl)-2methylpiperazin-1-yl]-2-oxoethoxy}phenyl)urea ([¹⁸F]4), a potent nonpeptide CCR1 antagonist, is described as a module-assisted two-step one-pot procedure. The final product was obtained utilizing the reductive amination of the formed 4-[¹⁸F]fluorobenaldehyde with a piperazine derivative and sodium cyanoborohydride. After HPLC purification of the final product ([¹⁸F]4, its solid phase extraction, formulation and sterile filtration, the isolated (not decay-corrected) radiochemical yields of ([¹⁸F]4 were between 7 and 13% (n=28). The time of the entire manufacturing process did not exceed 95 min. The radiochemical purity of ([¹⁸F]4 was higher than 95%, the chemical purity ≥60% and the enantiomeric purity >99.5%. The specific radioactivity was in the range of 59-226 GBq/µmol at starting radioactivities of 23.6-65.0 GBq ([¹⁸F]fluoride

The (2-methoxyphenyl)piperazine pharmacophore, a part of the WAY 100635 structure, has been functionalized with phosphinoarylbenzylamide or phosphinoarylbenzylamine chelator groups using propylene or hexylene alkyl chains as linkers (L2-L4). These heterofunctionalized phosphines bearing an arylpiperazine moiety have been used to stabilize rhenium tricarbonyl complexes of the type [Re(CO)(3)Br(kappa(2)-L)] (4, L = L2; 5, L = L3; 6, L = L4), which have been fully characterized, including by X-ray crystallographic analysis in the case of compounds 4 and 5. These monomeric complexes are six-coordinate, displaying a distorted octahedral coordination geometry with a facial arrangement of the carbonyl groups. The other three remaining positions are occupied by a bromide and by the bidentate heterofunctionalized phosphine, which coordinates through the phosphorus and the oxygen atom or through the phosphorus and the nitrogen atom in 4 and 5, respectively. The Tc-99m complexes (3a-6a!
) were also prepared and their characterization established by comparative HPLC, using the Re complexes as surrogates. The in vitro binding affinity for the 5HT(1A) receptor subtype and the selectivity against the 5HT(2A) receptors for the rheniurn complexes were determined. Compound 3 is the only one which presents a reasonable affinity and selectively towards 5HT(1A) (IC50 = 20 nM) and 5HT(2A) (IC50 = 4680 nM) receptors, respectively. When the spacer length between the chelate unit and receptor binding domain increased and/or the amide group in the chelator was replaced by a secondary amine unacceptable affinity values for 5HT(1A) receptors (IC50 = 200-1100 nM) and lost of selectivity were observed. (C) 2004 Elsevier B.V. All rights reserved.

Es werden neue Messergebnisse zur Fluoreszenz vom Americum(III) vorgestellt. Die Fluoreszenzzerfallszeit liegt im Nanosekundenbereich. Aufgrund der Analogie zum Curium(III) sollte auch beim Americum die Anzahl der Wassermoleküle in der Solvathülle die über die fluoreszenzzerfallskonstante ermittelt werden können. Es erschien aufgrund der Datenlage (Fluoreszenzzerfallszeit) ratsam, frühere Untersuchungen von Kimura zu wiederholen. Vorgestellt werden außerdem Untersuchungen zur Komplexbildung von Neptunium mit Vanillinsäure und von Kupfer(II) mit verschiedenen Dendrimeren.

This paper presents a theoretical study of oscillatory and rotational instabilities of a solid spherical body levitated electromagnetically in axisymmetric coils made of coaxial circular loops. We apply our previous theory to analyze the static and dynamic stability of the sample depending on the AC frequency and the position of the sample in the coils for several simple configurations. An original analytical approach is introduced employing a gauge transformation for the vector potential. First we calculate the spring constants which define the frequency of small-amplitude oscillations. For static stability the spring constants must be positive. Dynamic instabilities are characterized by critical AC frequencies which, when exceeded, may result either in a spin-up or oscillations with increasing amplitude. It is found that the critical frequencies increase with the non-uniformity of the field. We show that for a spherically harmonic field the critical frequency for the spin-up instability in a field of degree l coincides with the critical frequency for the oscillatory instability in a field of degree l+1.

Oxidiertes Uran ist ein mobiler Schadstoff, der auch mit verschiedenen Anionen wie Carbonat oder Sulfat wasserlösliche Komplexe bildet. Uranyl ist aber auch bekannt für seine hohe Affinität zu kolloidalen Fe-Oxyhydroxiden. Derartige Kolloide entfernen bei pH 5…8 sehr effektiv U(VI) aus der Lösung, da sie aufgrund ihrer geringen elektrostati-schen Stabilität leicht agglomerieren. Diese Reaktion kann bei Altlasten aus dem Uran-bergbau die Ausbreitung des Urans verringern, wenn saures Minenwasser z. B. durch Vermischung mit neutralem, oxischem Grundwasser entsäuert wird. Für zuverlässige Vorhersagen der Migration des Urans benötigt man Informationen über die Struktur und Stabilität der Uranbindung auf molekularer Ebene. Art und Struktur der Sorptionsspezies sind bis heute nicht vollständig geklärt.

Hauptziel dieser Arbeit ist die strukturelle Aufklärung der sorptiven Bindung von Uranyl an Kolloide in Bergwerkswässern. Wir untersuchten auch die Mitwirkung der anwesenden Hauptionen Sulfat, Silikat und Carbonat bei der Sorption von Uranyl an das Modellkolloid Ferrihydrit (Fh), um zu prüfen, ob ternäre Oberflächenkomplexe entstehen.

Die EXAFS-Resultate legen nahe, dass Uranyl bei den hier simulierten Bedingungen (pH 5.5) Oberflächenkomplexe mit Ferrihydrit-Kolloiden bildet, an denen Sulfat, Silikat oder Nitrat unbeteiligt sind. Die durch ATR-IR nachgewiesenen U(VI)-Carbonat-Oberflächenkomplexe sind mit EXAFS nicht zu erkennen. Eine mögliche Erklärung wä-re, dass Carbonat monodentat mit Uranyl verknüpft ist. Gegenwärtig prüfen wir, ob ein solcher Komplex mit EXAFS verifiziert werden kann. Unabhängig davon lassen sich die experimentellen EXAFS-Daten durch einen binären Fh=UO22+-Komplex mit neuer räumlicher Anordnung erklären. Zukünftige Untersuchungen befassen sich auch mit der Langzeitstabilität der Uranbindung.

While many laboratories plan to use TESLA-like cavities and/or cryomodules in CW regime, the TTF-III coupler [1] has never been tested in CW mode to find out what is its average power limit and what parts of the coupler would require upgrade/redesign for higher average power operation. ACCEL, BESSY, Cornell, DESY and Rossendorf agreed to collaborate on such a test of the TTF-III coupler. ACCEL manufactured one TTF-III coupler free of charge and assembled it on the test stand in clean-room condition. DESY provided the test stand, some additional hardware and its “know-how” in testing TTF-III couplers. Cornell provided IR viewports, instrumentation feedthroughs and its expertise and help during the coupler test and tried to coordinate joint efforts. BESSY participated in the test and offered a follow-up test in the new HoBiCaT horizontal test facility [2]. The test happened at Rossendorf at their 10 kWCW klystron test transmitter from June 14 to June 18.

The superconducting linear accelerator ELBE has a 200W at 1.8 K cryogenic plant. Two cold compressors are used for recompression of the Helium at the 4 K level and for stabilising the pressure in the accelerator cryostat. The talk will give an overview over the ELBE cryogenic system and will focus on the operation experience with the cold compressor system and the filling modes of the cryostat. Specific problems of the ELBE Helium plant concerning purity, maintenance and reliability will be discussed.

We report on time resolved femtosecond carrier dynamics in molecular beam epitaxy (MBE) grown GaNxAs1-x with a nitrogen fraction of 1.3 %. The intraband carrier relaxation time in GaNxAs1-x is found to be significantly larger than in GaAs. We compare the experimental results with carrier ? polar optical phonon scattering rates calculated within the band anticrossing model. From the results we conclude that the slowing down of the carrier relaxation is a result of the strongly modified band structure in GaNxAs1-x.

The investigation of the well documented different irradiation/annealing states of the four former Greifswald units are a special advantage to assess the reactor pressure vessel integrity and to check the corresponding rules.
The results of new, more accurate calculations of the neutron fluence will be given. Further, the change of the RPV dismantling strategy requires a new approach for the trepanning procedure. The new procedure will be shortly described as well as some aspects of the material investigation program.

Risikoabschätzungen zur Migration von Schadstoffen durch geologische Formationen über den Wasserpfad unterscheiden zwischen mobilen und immobilen Schadstoffen. Die Schadstoffmobilität kann durch Kolloide beeinflußt werden. Die wichtigste Ursache für anorganische Kolloide in der Natur ist die Präzipitation von Sekundärmineralien. Verschiedene Publikationen existieren bereits zur Sekundärmineralkolloidbildung im Bulk von Wässern durch chemische Reaktionen nach der Mischung von Wässern unterschiedlicher Zusammensetzung oder nach dem Zutritt von Luft zu vorher isolierten Wässern. Die direkte Bildung von eisenhaltigen Sekundärmineralkolloiden an der Gestein-Wasser-Grenzfläche durch die Verwitterung von Gesteinsmaterial ist eine Alternative zum bekannten Kolloidbildungsmechanismus im Bulk von Wässern. Dieser Mechanismus ist von Bedeutung für die Kolloidentstehung bei der Verwitterung von frisch zerkleinertem Gestein in der ungesättigten Zone wie z. B. Gestein in Bergwerkshalden. Auch die nach diesem Mechanismus gebildeten eisenhaltigen Kolloide können den Transport von Schadstoffen beeinflussen, denn sie besitzen eine große spezifische Oberfläche und eine hohe Sorptionsaffinität.

This paper describes the development of a thermal model for flash lamp processing of 3C-SiC on silicon substrates in the millisecond regime, the FLASiC process. The model is a numerical solution of the enthalpy equation, using a modified implicit Crank-Nicholson scheme to combine accurate prediction of melt depths with reasonable computation times. The model has been calibrated against experiments and then used to compute the temperature distribution in the wafer during annealing. The results show the time and extent of melting as a function of layer thickness, wafer preheat temperature, and pulse intensity and duration. The kinetics of melting and regrowth have also been considered.

Der Erfindung liegt die Aufgabe zugrunde, die Erzeugung eines Elektronenstrahls mit einer extrem großen mittlerer Leistung und einer kleinen Emittanz mit einem einfachen HF-Koppler und geringen Kosten bei koaxialer Einkopplung und variabler externer Güte sowie geringer thermischer Belastung des supraleitenden Resonators zu erreichen.

Die Strahlungsquelle kann im Frequenzbereich von 10 GHz bis 50 THz arbeiten und spezielle Parameter erfüllen.

Es werden Instabilitäten gedämpft und das Kornwachstum während der Erstarrung von Legierungen gesteuert.

Es ist ein Sensor dargestellt, der in der Lage ist, die Stoffzusammensetzung mittels faseroptischer Refrakometrie an einer Vielzahl räumlicher Punkte eines Untersuchungsvolumens gleichzeitig zu messen, ohne eine Vielzahl von Anordnungen zu verwenden.

Es wird eine kostengünstig zu realisierende und zuverlässig arbeitende Armatur in Rohrleitungssystemen angegeben.

Es werden radiolytisch und metabolisch stabile Metallkomplexe vorgeschlagen, die zur Konjugation mit Biomolekülen geeignet sind sowie ein Verfahren zu ihrer Herstellung.

Es wird eine Quanten-Kaskaden-Laser-Struktur zur Verfügung gestellt, welche die Herstellung von Quanten-Kaskaden-Lasern, die bei Zimmertemperatur emittieren können, ermöglicht.

Es wird die Fehlerquote bei der in-beam PET weiter gesenkt, in dem ihre statistische Sicherheit erhöht wird.

Mit der Erfindung soll die Effektivität der supraleitenden HF-Fotoelektrode und die Strahleigenschaft, insbesondere die transversale Emittanz, für mittlere und hohe Leistungen verbessert werden.

Mit der Erfindung wird erreicht, dass die sprunghafte Veränderung des übertragenen Drehmnoments nicht mehr oder in sehr abeschwächter Form geschieht und die Drehmomentveränderung über dem Drehzahlverhältnis zwischen Pumpen- und Turbinenrad weitgehend kontinuierlich erfolgt.

For several years Be-7 measurements have been conducted at high-altitude stations in Austria (Sonnblick, 3106 m), Switzerland (Jungfraujoch, 3580 m), Germany (Zugspitze, 2962 m), and Italy (Mt. Cimone 2165 m) with the aim to support a study on vertical ozone transport in the Alps (VOTALP project).
Aerosol samples, collected on filtering media with high volume samplers, are analysed for Be-7 by high-resolution gamma-spectrometry.
Prior to evalution of the Be-7 time series of the four stations, both sampling and measurement procedures were cheked for comparibility. The results of an intercomparison exercise performed within the mentioned project are reported.

The non-linear optical properties of solid state materials in the THz frequency region are to a large extent unexplored due to missing high-intensity coherent light sources in this frequency range. Although recent advances in table-top laser based THz systems have been enormous, free-electron lasers (FEL) are at present still the only tunable lasers which provide high peak intensities and a sufficient narrow spectral width to perform nonlinear spectroscopy at THz frequencies. Recently we investigated the dispersion of the second order nonlinear susceptibility (c(2)) in thin GaAs crystals below the optical phonon resonance via second harmonic generation (SHG) experiments with an FEL [1]. These experiments provide insight into the relative contributions of higher-order cohesive lattice forces to c(2). The nonlinear optical susceptibility in polar semiconductors in the THz frequency range is strongly influenced by the presence of optical phonons and should exhibit several peculiarities: A strong resonant enhancement of the SHG at half the frequency of the TO phonon (8.0 THz in GaAs) and at the TO phonon itself as well as a zero-crossing for frequencies between 4.0 THz and the TO phonon resonance due to the cancellation of higher order ionic and electronic contributions was predicted [2]. The experiments are performed with the THz FEL FELIX (Nieuwegein, Netherlands), which delivers picosecond pulses with µJ energy. We could observe both the resonance and the zero-crossing of c(2) below the Reststrahlen-band for the first time. From the value obtained for the zero-crossing of the nonlinear susceptibility we conclude that the contribution of the phonon interaction through the second-order lattice dipole moment has to be significantly smaller and the contribution from the third-order lattice potential anharmonicity has to be larger than determined previously [3]. Besides the relevance for the THz nonlinear susceptibility these terms are also important for two-phonon sidebands in the infrared absorption, phonon decay [3] and for a quantitative description of Raman spectra [4]. We propose that SHG below the optical phonon resonance is an elegant method to quantitatively determine the higher-order potential contributions to the nonlinear susceptibility.

[1] T. Dekorsy et al., Phys. Rev. Lett. 90, 055508 (2003).
[2] A. Mayer and F. Keilmann, Phys. Rev B 33, 6954 (1986).
[3] C. Flytzanis, Phys. Rev. B 6, 1264 (1972); Phys. Rev. Lett. 29, 772 (1972).
[4] S. Go, H. Bilz, and M. Cardona, Phys. Rev. Lett. 34, 580 (1975).

Summary: The palladium-mediated N-arylation of indoles with 4-[¹⁸F]fluoroiodobenzene as a novel radiolabelling method has been developed. Optimized reaction conditions were elaborated by variation of different catalyst systems (CuI/1,2-diamines and Pd₂(dba)₃/phosphine ligands), based and solvents in the reaction of indole with 4-[¹⁸F]fluoroiodobenzene. Optimized reaction conditions (Pd₂(dba)₃/(2-(dicyclohexyl-phosphino)-2´-(N,N-dimethylamino)-biphenyl, NaOBu^t, toluene, 100 °C for 20 min) were applied for the synthesis of ¹⁸F-labelled σ₂ receptor ligands [¹⁸F]-11 and [¹⁸F]-13 which were obtained in 91 and 84 % radiochemical yields, respectively.

The hypothetical scenario of a severe accident with core meltdown and formation of a melt pool in the lower plenum of a Light Water Reactor Pressure Vessel (RPV) can result in the failure of the RPV and the discharging of the melt to the containment. One accident management strategy could be to stabilize the in-vessel debris or melt pool configuration in the RPV as one major barrier against uncontrolled release of heat and radionuclides into the containment of the plant.
To obtain an improved understanding and knowledge of the melt pool convection, the vessel creep, possible failure processes and modes occurring during the late phase of a core melt down accident the FOREVER-experiments have been performed at the Division of Nuclear Power Safety of the Royal Institute of Technology, Stockholm. These experiments were simulating the behavior of the lower head of the RPV under the thermal loads of a convecting melt pool with decay heating.
An axisymmetric Finite Element (FE) model was developed to simulate these experiments. First the temperature field within the melt pool and within the vessel wall was calculated with a CFD-Model. But due to the lack of a turbulence model for very high internal Rayleigh numbers of up to 1017 in the prototypic case and due to the very time consuming CFD-solution, the Effective Conductivity Convectivity Model (ECCM) as proposed by Bui has been implemented. Once the temperature field in the vessel wall is evaluated, the transient structural mechanical calculations are then performed applying a creep model which takes into account the large temperature, stress and strain variations. The creep model includes the primary, secondary and tertiary creep stages.
In the prior work only a one-way coupling between the thermal and the mechanical model was applied: first the transient temperature field was calculated and then the transient mechanical calculation was performed applying the appropriate temperature field at each time step. To take into account the melt level drop by thermal expansion the initial level was lowered “by hand”. The feedback from the viscoplastic deformation to the temperature field was not correctly considered in the one-way coupling. On the other hand the earlier investigations showed that slight temperature shifts of only 10 K at an overall temperature level clearly above 1000 K had significant effects concerning the failure time of the vessel.
To overcome the disadvantages of the single coupling model a new recursively coupled model is developed. This paper deals with the new results and so far the results show that a recursively coupled thermal and mechanical solution is closer to reality than a single coupled model where the mechanical deformations have no impact to the thermal model. Due to the scaling effect it is expected, that the fully coupled model is necessary to be able to perform reliable best estimate calculations for prototypic light water reactor scenarios.