Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

Transmission radiometry with photon or particle radiation is a common technique for the measurement of thickness, density and composition of materials, e.g. in production lines and in multiphase flow metering. Moreover, radiation transmission measurement is the basis for many imaging techniques, such as x-ray and gamma ray tomography. A common problem associated with transmission measurement is correct temporal averaging for time-varying material properties. Averaging the intensity signal at the detector over time and taking this mean to calculate average ray attenuation leads to incorrect results when attenuation changes within the integration period. This paper discusses the implications of this systematic error and introduces a methodology for correct averaging which is applicable even to very low intensity measurements.

Surface pattern on Ge induced by Bi cluster ions doffer drastically from morphology after monomer irradiation. Large aspect ratios of dots and ripples and crystalline surfaces after cluster irradiation have been observed. A novel patterning mechanism explains the dot formation qualitatively by means of local tiny melt pools induced by ion impact . Moreover this model predicts the formation of dot pattern even for monomer irradiation at elevated temperature. The aim of this work is to investigate the pattern formation by heavy Bi monomer bombardment. Surface pattern obtained at room temperature and under normal incidence are investigated in an ion energy range from 4 to 60 keV. A energy driven pattern transition from hole over dot to sponge like structures is observed. Moreover, the pattern formation by Bi monomer ions is investigated at elevated temperatures showing a energy dependent transition from sponge to dot like pattern.

Due to the huge excess of natural nanoparticles, the identification and quantification of engineered nanoparticles is a big challenge to the analyst. Moreover, identification in a qualitative sense and quantification by mass concentration alone is not sufficient since the potential environmental hazard arising from engineered nanoparticles is controlled by a number of further properties of the particles. The most important methods of nanoparticle fractionation and nanoparticle detection are discussed. It is shown that coupled techniques are increasingly applied. Dedicated techniques that are tailored to the search for a certain targeted engineered nanoparticle are more promising than universal approaches that aim at the search for any engineered nanoparticles. Analyses should not rely on only one method but several complementary methods should be used.

We present a microfluidic cell plate for endocrine disrupting chemicals (EDCs) detection, like estrogenic activity, in waterish solution. This platform technology consists of four independent micro flow units made of polydimethylsiloxane (PDMS) and glass, which enables a selective detection of up to four species of the EDCs per one-way chip containing the corresponding immobilized receptor. The concept of the detection is based on direct fluorescence analysis. In order to found out the electrical parameters of the microfluidic system electroluminescence (EL) measurements as a function of the concentration of the QD800 dye were investigated. Finally, the microfluidic device was attached to the flow control system. Different edge filters were tested in order to attenuate the MOSLED light signal and to maximize the QD800 dye signal at 800 nm which works best for a 780 nm edge filter. Measurements using an integrated photo diode as detector were performed to point out the relationship between the dark and photo current.

Scanning ion microscopy (SIM) based on secondary electron (SE) imaging initiated by focused ion beam (FIB) irradiation of surfaces can yield important information about the topography, the material changes or crystallographic orientations of a specimen. Compared to a scanning electron microscope (SEM) based on a similar principle the information comes from a very near surface region due to the small penetration depth of the ions. A disadvantage of the SIM is the lower spatial resolution and the fact that energetic ions damage the surface during imaging by implantation and sputtering processes.
The aim of this work is to investigate the behavior of a mass-separated FIB working with a bismuth liquid metal ion source which emits a broad spectrum of single and double charged monomers as well as cluster ions in the frame of the examination of the self-organization of nano-pattern on surfaces under heavy ion erosion [3]. The study of all interactions of the primary beam within the surface and the knowledge of the fundamental parameters leads to a more correct interpretation of the secondary electron images.

Background
Due to the progression of uranium content in the bio-sphere at present, uranium is expected to be increasingly accumulated in the food chain and eventually in the living organisms. To get valuable information and to understand its toxicity, behaviour and distribution in such cellular level; knowledge about uranium (VI) speciation in biosystems will be useful for evaluating toxicity after uranium exposure. Little is known about interaction and behaviour of uranium with some biomolecules (e.g. urea and uric acid) that commonly present in biological fluids or in bio-system. In attempt to provide information in this context, we investigate some important thermodynamic data upon complexation of uranium with some single bioligands, viz., uric acid using TRLFS.

Investigations to the mobilisation of radionuclides are essential in the risk assessment of radionuclides in the environment and the safety assessment of nuclear waste repositories. The mobilisation of radionuclides takes place for instance by the formation of water soluble complexes or sorption processes on mineral surfaces. Concerning the required risk and safety assessments a wide knowledge about the chemical and physical behavior of radionuclides, particularly actinides, is needed. Thus, interaction studies of radionuclides are carried out, e.g. complexation studies with components of the environmental compartments (humic acids, bioligands, inorganic ligands, bacteria, …).
Borates (e.g. boric acid B(OH)3 and its salts or esters) are ubiquitous compounds in the environment (rocks, soils, natural waters) and are used in many applications, e.g. glass production, detergents, agriculture and nuclear technology. Thus, there are many sources for the release of borates in the environment. But although there is a relevance of borates in the environment and, perhaps, in nuclear waste repositories, the Ln(III)/An(III)-borate system is investigated insufficiently.
The work concentrates on the complex formation in the An(III)/Ln(III)-borate system. The influence of temperature and ionic strength on the complexation will be investigated.

RUTA-70 is a pool type reactor with the rated power of 70 MW designed as a district heat supplying facility. The basic design principles of this reactor are simplicity of the design and a high safety level due to a low pressure and a large coolant inventory in the primary system. The core design with the CERMET fuel rods also contributes to the reactor safety due to a high thermal conductivity of the fuel matrix and its role as the additional barrier to the fission products release.

RUTA-70 model for simulations with the internally coupled code systems DYN3D/ATHLET and DYN3D/RELAP5 was developed. A 3-D power distribution in the core is calculated by DYN3D with thermal-hydraulic feedback from the system codes. The reactor facility model includes reactor pool, two reactor loops, circulation pumps, primary and the secondary heat exchangers and core channels. The core model consists of 16 fuel assemblies in the 60-degree symmetry sector with different burnable absorber (Gd) concentrations.

The steady-state with the rated reactor parameters and a BDB accident scenario were simulated with the DYN3D/ATHLET and DYN3D/RELAP5 coupled code systems to verify these codes. The simulated accident is initiated by the trip of two operating primary circulation pumps. Additionally to the initial event the SCRAM failure is postulated.

The compared codes give close predictions for the initial and final states of the accident but not for the transition between them. The observed deviations are explained by differences in the subcooled boiling models of the system codes ATHLET and RELAP5. Both simulations confirm a high level of the reactor inherent safety. The allowed safety margins were not reached.

The effect of uniform magnetic fields on hydrogen evolution reaction during metal deposition and water electrolysis was investigated by means of electrochemical techniques coupled with in-situ microscopic observation, velocity measurements and numeric simulation. The desorption of hydrogen bubbles is enhanced in applied magnetic fields independent on their orientation relative to electrode surface. The origin of this effect is attributed to Lorentz force driven convection generated by the applied magnetic field.

The relative influence of the Lorentz force and the magnetic gradient force on micro-structured copper deposition is studied with simple magnetic elements consisting of cylindrical permanent magnets are placed closely behind the surface of the cathode. Analytical findings and numerical simulations reveal that for magnets of small diameter the magnetic gradient force dominates. Experimental investigations find that the thickness of the deposited copper layer increases in the vicinity of the magnets. The combined analysis of simulations and experiments shows that this enhancement of mass transfer results from a local convection towards the electrode which is forced by the magnetic gradient force.

DYN3D is a three-dimensional nodal diffusion code for steady-state and transient analyses of Light-Water Reactors (LWRs) with square and hexagonal fuel assembly geometries. Currently, several versions of the DYN3D code are available including a multi-group diffusion and a simplified P3 (SP3) neutron transport option. In this work, the multi-group SP3 method based on trigonal-z geometry was developed. The method is applicable to the analysis of reactor cores with hexagonal fuel assemblies and allows flexible mesh refinement, which is of particular importance for VVER-type Pressurized Water Reactors (PWRs) as well as for innovative reactor concepts including block type High-Temperature Reactors (HTRs) and Sodium Fast Reactors (SFRs). In this paper, the theoretical background for the trigonal SP3 methodology is outlined and the results of a preliminary verification analysis are presented by means of a simplified VVER-440 core test example. The accordant cross sections and reference solutions were produced by the Monte Carlo code SERPENT. The DYN3D results are in good agreement with the reference solutions. The average deviation in the nodal power distribution is about 1%.

The 7th dynamic benchmark is the most recent problem specified within the AER activities on verification of the coupled neutronic/thermal-hydraulic codes. This is the VVER-440 transient initiated by re-connection of the isolated reactor circulation loop filled with a low-temperature coolant. During the transient a core power excursion with a non-symmetric radial distribution is expected due to incomplete coolant mixing at the core inlet.

The externally coupled code system DYN3D/ATHLET developed in HZDR was used in the benchmark simulation. In the case of external coupling all neutronic and thermal-hydraulic parameters of the core are calculated by the 3D code of neutron kinetics DYN3D.

The computer model of the VVER-440 reactor used in the AER-7 calculations represents a modified version of the earlier developed input deck for the AER-6 benchmark simulation. The model includes 6 reactor loops with the main circulation pumps and steam generators. The secondary system is modelled up to the turbine valves. The 3D core model includes all 349 fuel assemblies (assembly-by-assembly approach).

The main results of the benchmark calculation are presented and discussed.

Metal-oxide-semiconductor capacitors containing the alternative high-k dielectric LaLuO₃ were treated by flash lamp annealing (FLA). Capacitance–voltage (C–V) and current–voltage (J–V) characteristics reveal an increase in the capacitance for the flashed samples while the very low leakage current of the LaLuO₃ is retained. Microstructural investigations confirm the thermal stability of the film even after FLA at 1200 °C, 20 ms.

We investigate the separated flow around an inclined flat plate at a Reynolds number of 10⁴ by Direct Numerical Simulation (DNS) and time-resolved Particle Image Velocity (PIV). Flow separation is suppressed using sinusoidally and rectangularly oscillating Lorentz forces in streamwise direction. An rms momentum coefficient of 2.25% increases the time-averaged lift, deduced from PIV by a global momentum approach, by 20–45%. Whereas sinusoidal forcing increases both lift and drag, rectangular waves create no significant additional drag. Analysis of the DNS flow structures reveals different immediate vortex dynamics induced by the actuation.

Radiation therapy is an important treatment modality in cancer therapy. New radiation species, like protons and light ions have the potential of increasing tumor conformality of irradiation. Because of the way these particles deposit their energy on their path through tissue they allow for an increased dose deposition in the tumor volume and reduce the damage of the surrounding healthy tissue. Such high precision radiotherapy treatment requires efficient quality assurance techniques. Small changes in the irradiated volume will lead to a mismatch of the deposited dose maximum and the tumor. This causes missing dose in the tumor volume and potential damage to healthy tissue. Therefore, a dose monitoring system is highly desirable. Between 1997 and 2008, the in-beam Positron Emission Tomography (PET) method was used at the GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, Germany, for monitoring the dose delivered by 12C beams. Since the positive clinical impact of the method has been shown at the Dresden Proton Therapy facility an in-room PET/CT will be installed for the same purpose.
Due to inherent limitations of this method, a direct quantification of the delivered dose is not feasible. Therefore, another approach based on dose monitoring by detection of prompt gamma rays is currently under investigation. For this purpose a Compton camera design was evaluated with respect to the special requirements and conditions that arise from this application. Different concepts were compared by means of simulation. Now the construction of a first prototype is under way.

There has been a recent revival of interest in Th-based fuel cycles, particularly for commercial Pressurized Water Reactors (PWR), motivated primarily by their potential to address concerns related to the proliferation potential, saving of natural uranium resources, and waste disposal of the conventional uranium fuel cycle. The objective of this talk is to provide an overview of some of the recent studies examining implementation scenarios, potential benefits and drawbacks associated with the use of Th-based fuels in current generation of PWRs.

The magnetorotational instability (MRI) triggers turbulence and enables outward transport of angular momentum in hydrodynamically stable accretion discs. By using theWKB approximation and methods of singular function theory, we resolve two different paradoxes of MRI that appear in the limits of infinite and vanishing magnetic Prandtl number. For the latter case we derive a new strict limit of the critical Rossby number. This new limit of Roc = −0.802, which appears for a finite Lundquist number of Lu= 0.618, extends the formerly known inductionless Liu limit of Roc = −0.828 valid at Lu = 0.

The magnetorotational instability (MRI) triggers turbulence and enables outward transport of angular momentum in hydrodynamically stable rotating shear flows, e.g., in Couette-Taylor cells and in accretion disks. What laws of differential rotation are susceptible to the destabilization by the axial or helical magnetic field? The answer to this vital for astrophysical and experimental applications question inevitably leads to the study of spectral and geometrical singularities on the instability threshold. The singularities provide a connection between seemingly discontinuous stability criteria and thus explain paradoxes in the theory of MRI that were kept poorly understood since 1950s. By using the WKB approximation and methods of singular function theory, we resolve two different paradoxes of magnetorotational instability that appear in the limits of infinite and vanishing magnetic Prandtl number. For the latter case we derive a new strict limit of the critical Rossby number. This new limit of Roc = −0.802, which appears for a finite Lundquist number of Lu = 0.618, extends the formerly known inductionless Liu limit of Roc = −0.828 valid at Lu = 0.

Structural optimization of non-conservative systems with respect to stability criteria is a research area with important applications in fluid-structure interactions, friction-induced instabilities, and civil engineering. In contrast to optimization of conservative systems where rigorously proven optimal solutions in buckling problems have been found, for nonconservative optimization problems only numerically optimized designs have been reported. The proof of optimality in non-conservative optimization problems is a mathematical challenge related to multiple eigenvalues, singularities in the stability domain, and non-convexity of the merit functional. We present here a study of optimal mass distribution in a classical Ziegler pendulum where local and global extrema can be found explicitly. In particular, for the undamped case, the two maxima of the critical flutter load correspond to a vanishing mass either in a joint or at the free end of the pendulum; in the minimum, the ratio of the masses is equal to the ratio of the stiffness coefficients. The role of the singularities on the stability boundary in the optimization is highlighted, and an extension to the damped case as well as to the case of higher degrees of freedom is discussed.

Magnetorotational instability (MRI) triggers turbulence and enables outward transport of angular momentum in hydrodynamically stable accretion discs. By using the WKB approximation and methods of singular function theory, we resolve two different paradoxes of MRI that appear in the limits of infinite and vanishing magnetic Prandtl number. For the latter case, we derive a strict limit of the critical Rossby number. This limit of Roc=−0.802, which appears for a finite Lundquist number of S=0.618, extends the formerly known inductionless Liu limit of Roc=−0.828 valid at S=0.

not available, please contact the author

TEM investigation contributing to the comprehension of superconductivity in Ga-doped Si

ZnO nanostructures are promising candidates for the development of novel electronic devices due to their unique electrical and optical properties. Here, we present a complementary electrical characterization of individual upright standing and lying ZnO nanorods using conductive atomic force microscopy (C-AFM). Initially, the electrical properties of the arrays of upright standing ZnO NRs were characterized using two-dimensional current maps. The current maps were recorded simultaneously with the topography acquired by contact mode AFM. Further, C-AFM was utilized to determine the local current-voltage (I-V) characteristics of the top and side facets of individual upright standing NRs. Current-voltage characterization revealed a characteristic similar to that of a Schottky diode. Detailed discussion of the electrical properties is based on local I-V curves, as well as on the 2D current maps recorded from specific areas.

Deep level traps in melt grown ZnO single crystal created by oxygen implantation and subsequent annealing in air were studied by deep level transient spectroscopy measurement between 80 and 300 K. The EC–0.29 eV trap (E3) was the dominant peak in the as-grown sample and no new defects were created in the as-O-implanted sample. The single peak feature of the deep level transient spectroscopy (DLTS) spectra did not change with the annealing temperature up to 750 °C, but the activation energy decreased to 0.22 eV. This was explained in terms of a thermally induced defect having a peak close to but inseparable from the original 0.29 eV peak. A systematic study on a wide range of the rate window for the DLTS measurement successfully separated the Arrhenius plot data originated from different traps. It was inferred that the E3 concentration in the samples did not change after the O-implantation. The traps at EC–0.11, EC–0.16 and EC–0.58 eV were created after annealing. The EC–0.16 eV trap was assigned to an intrinsic defect. No DLTS signal was found after the sample was annealed to 1200 °C.

Ausgehend von geeigneten Definitionen der zentralen Begriffe Zuverlässigkeit, Risiko und Sicherheit im technischen Sinn ergibt sich die grundsätzliche Möglichkeit der Bestimmung des Risikos für technische Systeme. Im Rahmen der Zuverlässigkeits- und Risikoanalyse können diese mathematisch belastbaren Definitionen auch die Stochastik von technischen Ausfällen und dadurch ausgelösten Unfällen berücksichtigen.
In Zusammenhang mit dem Sicherheitskonzept für deutsche Kernkraftwerke werden determinierte und probabilistische Methoden zur Bestimmung des Risikos bei der Nutzung der Kernenergie angewendet. Hierbei werden insbesondere auf das gestaffeltes Sicherheitskonzept, das Schutzzielkonzept sowie bestimmte Auslegungsprinzipien zur Verminderung des kerntechnischen Risikos eingegangen.
In einem weiteren Teil des Vortrages wird auf die Fragestellung im Umgang mit dem Restrisiko der kerntechnischen Nutzung eingegangen. Der Vergleich von wahrgenommenen mit tatsächlichen Risiken im technischen Bereich wie auch im Alltagsleben fällt häufig sehr unterschiedlich aus. Auch hängt die Akzeptanz eines Risikos sehr stark von einem zu erwartenden Nutzen ab.
Die methodische Darstellung von Risikoakzeptanz und Risikowahrnehmung auf der individuellen sowie auf der gesellschaftlichen Ebene ist nur im Rahmen komplexer Zusammenhänge möglich.

Many applications in plasmonics or sensorics require large scale arrays of nano-sized dot structures with rather high surface coverages. Typical dimensions, e.g., 50nm diameter, 200nm center-center distance, 1000µm × 1000µm arrays, quickly lead to extremely high numbers of objects in the design to be handled by both the software and the lithography system. In case of the aforementioned dimensions this would amount to be about 2.5 × 107 objects.

Using regular techniques the dots would be represented by a matrix of circles or dots in the design – or references to those, for that matter. Any changes in the layout of the structures would require a rather large effort since every object or reference would have to be edited. Additionally, with commonly used lithography systems the writing times quickly exceed reasonable values due to the beam settling times normally required for each object in the design. Even with values as low as 1ms the overall sum of the settling times would be roughly 7hrs. This is excluding the actual writing times!

The alternative method for the creation of ultra large scale nano dot arrays presented here is astonishingly simple and does not require any particular efforts: In electron beam lithography, exposure is based on single pixels – or dots – with defined distances (step size). The overlap of the single pixels yields the desired continuous structures. Thus, separating these pixels by the distance required for the lattice of nano dots, i.e., setting the step size to the lattice constant, would result in the desired lattice. This may be achieved by underexposing a regular rectangle by a factor of about 1/10 of the clearing dose, i.e., the result is a lattice of separated dots. The diameter of the dots may be adjusted within certain limits by the dose used for exposure.

As a result not only the writing times are strongly decreased – depending on the parameters many hours of processing time may be saved – but also handling of an array of dots is simplified to the action on rectangles or other shapes in the GDSII editor. No hassle with millions of dots is required.

As a proof of principle, different large lattices have been produced using a Raith 150TWO system in a lift-off process with PMMA or ZEP as resists on silicon. Additionally, a 4000µm × 4000µm lattice with a lattice constant of 500nm has been produced in an etching process with HSQ as the resist and reactive ion beam etching (RIBE) structuring gold on glas as a possible application for plasmonic sensors. Compared to the regular technique the processing times could be greatly reduced. The resulting samples show almost perfect lattices, the shape of the dots is also of good quality. Multiple exposures with shifted write fields also enables fabrication of hexagonal lattices or dipole structures.

Inspired by the setup of the von-K\'arm\'an-Sodium (VKS) dynamo experiment numerical simulations of the kinematic induction equation have been carried out in a cylindrical domain. A localized internal distribution of large relative permeability is considered that represents soft iron material within a conducting fluid flow.

So called paramagnetic pumping at the interface between fluid and soft iron causes a selective enhancement of the axisymmetric azimuthal field component, ultimately leading to a decoupling between poloidal and toroidal magnetic field. For moderate magnetic Reynolds numbers, the poloidal component decays faster than the toroidal part or the simplest non-axisymmetric mode ($m1$). This effect only concerns the necessarily decaying axisymmetric field and does not occur in case of a larger/smaller electrical conductivity.

The phenomenon requires a particular setup e.g. a thin disk-like permeability distribution and remains restricted to the axisymmetric field modes. However, these properties indeed apply to the VKS dynamo.

The separation of poloidal and toroidal modes might be important with regard to mean field dynamo models of the VKS dynamo since the decoupling effectively disrupts the possibility for a closure of the dynamo cycle. However, the separation of the axisymmetric field modes can be prevented by an non-axisymmetric permeability distribution, which might give a hint why dynamo action is absent in experiments where the fluid flow is driven by an impeller system composed of soft iron disks and stainless steel blades.

Vibrational spectroscopy potentially provides structural information of molecule complexes. Actinyl ions can be identified by the frequency of their antisymmetric stretching vibrational mode which generally correlates with the character of the molecular environment of the actinyl ion group.
In this study the sorption behavior and the formed complexes of Uranium(VI) on gibbsite in inert gas and ambient atmosphere were analyzed by means of ATR FT-IR spectroscopy.

The radioactive isotope Selenium-79 is a long-lived fission product found in nuclear waste. Due to its long half live of 3.27 ∙ 105 years [1] it is expected to be one of the most contributing isotopes concerning safety assessments of nuclear waste underground repositories. The control of the mobility and bioavailability of selenium is therefore of great importance for a safe disposal of radioactive waste.
One major process controlling selenium mobility and bioavailability is the adsorption onto mineral surfaces of both the geological and engineered barrier.
The present study focuses on the impact of temperature on the sorption of selenate (SeO42-) onto anatase (TiO2). The sorption of selenate onto anatase at different temperatures (25°C – 60°C) was investigated both with batch experiments and ATR-FT-IR spectroscopy. In order to explain possible differences in sorption at higher temperatures, the surface of the anatase was investigated.

We document Quaternary fluvial incision driven by fault-controlled surface deformation in the inverted intermontane Gökırmak Basin in the Central Pontide mountains along the northern margin of the Central Anatolian Plateau. In situ-produced ¹⁰Be, ²¹Ne and ³⁶Cl concentrations from gravel-covered fluvial terraces and pediment surfaces along the trunk stream of the basin (the Gökırmak River) yield model exposure ages ranging from 7.0 ± 0.6 ka to 337 ± 43 ka and average fluvial incision rates over the past ~340 ka of 0.28 ± 0.01 mm a^-1. Similarities between river incision rates and coastal uplift rates support the inference that regional uplift is responsible for the river incision. Model exposure ages of surfaces on deformed pediments along tributaries of the trunk stream range from 48 ± 4 ka to 96 ± 9 ka, demonstrating that the thrust faults responsible for the pediment deformation were active at least until those times, and possibly remained active afterwards. Together, our data demonstrate cumulative incision that is linked to active internal shortening and uplift of ~0.3 mm a^-1 in the Central Pontide orogenic wedge at the northern margin of the Central Anatolian Plateau.

Nach der Katastrophe in Fukushima im März 2011 beschloss die Bundesregierung den schrittweisen Ausstieg aus der Atomenergie bis zum Jahre 2022. Innerhalb dieser elf Jahre sollen die neun verbliebenen Atomkraftwerke vom Netz genommen werden. Aber in diesen Zeitraum wird es keine endgültige Lösung zum Thema der Endlagerung in Deutschland geben. Zurzeit werden die in Deutschland anfallenden radioaktiven Abfälle in Zwischenlager gebracht. Für schwach- und mittelradioaktive Stoffe sind es die Landessammelstellen der Bundesländer. Die Kernkraftwerke und Forschungseinrichtungen besitzen standortbezogene Zwischenlager. Die hochradioaktiven Abfälle aus der Wiederaufarbeitung abgebrannter Brennelemente werden nach der erteilten Genehmigung zur Aufbewahrung in den zwei zentralen Zwischenlagern in Ahaus und Gorleben gelagert.
Für die Genehmigung zum Bau eines Endlagers muss der Sicherheitsnachweis zur Endlagersicherheit geführt werden. Der umfassende Sicherheitsnachweis enthält die Aspekte der Errichtungs- und Betriebsphase (Sicherheitsnachweise für die Betriebsphase) und die Aspekte der Nachbetriebsphase im Langzeitsicherheitsnachweis. Im Langzeitsicherheitsnachweis werden alle qualitativen und quantitativen Analysen und Argumente zur Begründung der Sicherheit für die Nachbetriebsphase eines Endlagersystems zusammengeführt [1]. Der Langzeitsicherheitsnachweis unterteilt sich in:
­ - die Langzeitsicherheitsanalyse mit Konsequenzenanalyse,
­ - Aussagen zur Robustheit und Zuverlässigkeit der Sicherheitsbewertung,
­ - Ergänzende Argumente: Indikatoren, Analoga, etc.
Die Langzeitsicherheitsanalyse kann als die standortspezifische Analyse der Funktion des Endlagersystems im Hinblick auf die radiologischen Konsequenzen verstanden werden und beinhaltet die Untersuchung des zukünftigen Verhaltens eines verschlossenen Endlagers mit radioaktiven Abfällen innerhalb eines vorgegebenen Nachweiszeitraums (1 Million Jahre) [1].
Ziel der Langzeitsicherheitsanalyse ist es mögliche Ursachen und Abläufe einer Freisetzung von Radionukliden aus einem verschlossenen Endlager sowie deren zukünftige Auswirkungen auf die Umwelt und die Bevölkerung vorherzusagen.
Die derzeitig sicherste Entsorgung für radioaktive Stoffe ist die Endlagerung in tiefen geologischen Formationen [2]. Diese Lagerung weist ein Multibarrierensystem auf, welches die radioaktiven Abfälle von der Biosphäre isolieren soll. Ein aus mehreren unabhängigen Barrieren bestehendes System soll den Schadstoffaustrag aus dem Endlager wirkungsvoll verhindern [3]. Es setzt sich zusammen aus:
­ - Technische Barriere
o Brennstoffmatrix
o Container
­ - Geotechnische Barriere
o Verfüllung der Bohrlöcher
o Untertägiges Dammsystem
o Verfüllung des Schachtsystems
­ - Geologische Barriere
o Wirtsformation (Salz, Granit, Ton)
o Deckgebirge mit Aquifersystem
In der Langzeitsicherheitsanalyse wird angenommen, dass es im Endlager zum Wassereintritt kommt. Dies hat zur Folge, dass die Behälter korrosiv zersetzt werden und es zur Auflösung der Abfallmatrix kommt. Infolgedessen können die Radionuklide mobilisiert werden und durch die verschiedenen Barrieren in die Biosphäre gelangen. Während des Transportes von der Geo- zur Biosphäre können die freigesetzten Radionuklide eine Vielzahl von Wechselwirkungen eingehen. Dabei spielen neben ihrem Komplexbildung-, Sorption- und Diffusionsverhalten, die Kolloidbildung und die Wechselwirkungen mit Mikroorganismen, Biofilmen, Pflanzen und letztendlich mit dem menschlichen Organismus die wichtigsten Rollen. Wir, das Institut für Radiochemie, wollen mit Hilfe unserer umfangreichen analytischen Möglichkeiten zur Identifizierung und Beschreibung der ablaufenden Prozesse beitragen. An fünf Beispielen sollen die verschiedenen Arbeiten im Institut für Radiochemie (IRC) näher vorgestellt werden.

1. Fein, E., I. Müller-Lyda, and A. Rübel, Endlagerung wärmeentwickelnder radioaktiver Abfälle in Deutschland, in Wissenschaftlich-Technische Berichte GRS-247. 2008, Gesellschaft für Anlagen- und Reaktorsicherheit mbH: Braunschweig / Darmstadt.
2. Auswahlverfahren für Endlagerstandorte, Empfehlungen des AkEnd – Arbeitskreis Auswahlverfahren Endlagerstandorte. 2002: (www.akend.de).
3. Geckeis, H., V. Metz, and B. Kienzler, Geochemisches Verhalten der Radionuklide im Multibarrierensystem nuklearer Endlager. Nachrichten - Forschungszentrum Karlsruhe, 2004. 36(2): p. 110-115.

For the safety assessment of high-level nuclear waste repositories in deep geologic formations, the understanding of actinide migration behaviour is one of the most important issues. In recent decades, the solution chemistry, e.g. hydrolysis [1], complexation with inorganic ligands [1], but also the interactions of the actinides at interfaces with the geo- and biosphere have been intensely investigated [2]. However, because of the experimental difficulties, only few studies have been performed at temperatures outside the range 20 – 30°C which hampers the prediction of actinide reactive transport in the environment of heat generating high-level nuclear waste repositories.
The speciation of (radioactive) metal ions in solution will be affected by the thermal conditions, since the properties of water, e.g. density, dielectric constant, viscosity, ion product, are altered with temperature and pressure [3,4].
The formation and distribution of U(VI) hydrolysis species is predicted to depend strongly on the temperature. In particular the stability of U(VI) polynuclear hydroxo complexes, which are dominant species at 25°C may change. According to experimental studies of other metal ions, namely Al(III) and La(III), the nuclearity of polynuclear complexes decreases upon increasing temperature [5,6]. At 25°C several spectroscopic techniques, namely UV-vis, TRLFS, EXAFS and vibrational spectroscopy have been applied for identification and structural characterization of U(VI) hydroxo species [7-10]. At elevated temperatures, TRLFS was used for the determination of luminescent characteristics of single hydroxo species as a function of the temperature [11,12]. But, approaches to examine alterations in the thermodynamic data itself are rare.
In this study, we investigate the U(VI) hydrolysis reactions up to 60°C using a multi-methodical approach by application of TRLFS and ATR FT-IR spectroscopy. The spectral data is compared to computed speciation patterns based on state-of-the-art thermodynamic models.

1.Guillaumont, R. et al., Update on the chemical thermodynamics of uranium, neptunium, plutonium, americium and technetium. Chemical Thermodynamics Vol. 5, OECD Nuclear Energy Agency, Elsevier (2003).
2.Brendler, V. et al., RES3T-Rossendorf expert system for surface and sorption thermodynamics, Journal of Contaminant Hydrology 281-291 (2003).
3.Marshall, W.L. et al., Io product of water substance, 0 - 1000°C, 1-10,000 bars - New international formulation and its background, Journal of Physical and Chemical Reference Data 2, 295-304 (1981).
4.Fernandez, D.P. et al., A formulation for the static permittivity of water and steam at temperatures from 238 K to 873 K at pressures up to 1200 MPa, including derivatives and Debye-Huckel coefficients, Journal of Physical and Chemical Reference Data 4, 1125-1166 (1997).
5.Mesmer, R.E. et al., Acidity measurements at elevated temperatures. 5. Aluminum ion hydrolysis, Inorg. Chem. 10, 2290-2296 (1971).
6.Ciavatta, L. et al., The hydrolysis of the La(II) ion in aqueous perchlorate solution at 60°C, Polyhedron 6, 1283-1290 (1987).
7.Meinrath, G., Uranium(VI) speciation by spectroscopy, J. Radioanal. Nucl. Chem. 1-2, 119-126 (1997).
8.Moulin, C. et al., Time-resolved laser-induced fluorescence as a unique tool for low-level uranium speciation, Appl. Spectrosc. 4, 528-535 (1998).
9.Müller, K. et al., Aqueous uranium(VI) hydrolysis species characterized by attenuated total reflection Fourier-transform infrared spectroscopy, Inorg. Chem. 21, 10127-10134 (2008).
10.Tsushima, S. et al., Stoichiometry and structure of uranyl(VI) hydroxo dimer and trimer complexes in aqueous solution, Inorg. Chem. 25, 10819-10826 (2007).
11.Eliet, V. et al., Time-resolved laser-induced fluorescence of uranium(VI) hydroxo-complexes at different temperatures, Appl. Spectrosc. 1, 99-105 (2000).

SnO₂ films were implanted with ⁵⁷Fe at substrate temperatures of room temperature and 300°C. The chemical states of Fe and Sn were characterized by ⁵⁷Fe CEMS and ¹¹⁹Sn CEMS, respectively. The implanted Fe species exist as Fe(II) and Fe(III) in SnO₂ films, which also are reduced into Sn(II)on the implanted surface. The as prepared and post annealed at 500°C samples did not show Kerr effect, but the sample implanted with 1 × 10¹⁷ Fe ions/cm² at 300°C showed Kerr effect although magnetic sextets were not clearly observed in the ⁵⁷Fe CEM spectra. The Kerr effect disappeared after annealing. It suggests that the number of magnetic defects decreases by absorption of oxygen. Magnetic relaxation appeared in the case of low implantation of 5 × 10¹⁶ Fe ions/cm², which is considered to be due to antiferromagnetism or paramagnetic relaxation.

We report on the fabrication of the planar waveguides in the Bi₄Ge₃O₁₂ crystal by using 17 MeV C⁵⁺ or O⁵⁺ ions at a fluence of 2×10¹⁴ ions/cm². The reconstructed refractive index profiles of the waveguides produced by either C⁵⁺ or O⁵⁺ irradiation are the “well” + “barrier” pattern distribution. The two-dimensional modal profiles of the planar waveguides, measured by using the end-coupling arrangement, are in good agreement with the simulated modal distributions. After thermal annealing treatment at 260°C for 30 min, the propagation loss for C⁵⁺ and O⁵⁺ irradiated waveguides could be reduced down to ~1.1 dB/cm and ~4.8 dB/cm, respectively, which exhibit acceptable guiding qualities for potential applications in integrated optics.

Migration of radionuclides out of a salt-based repository requires transport pathways, where substances propagate by molecular diffusion or even pressure-driven advection. Diffusion coefficients and permeability, being very low in most intact saline rocks, are likely to increase considerably under geomechanical stress, inevitably occurring for instance in the excavation damage zone. Observation and evaluation of transport processes in such heterogeneously structured materials are most demanding, because they likely occur in either extremely localized, macroscopic but rare fractures or in dispersed, mostly indiscernible but still connected microscopic voids.
Applying salt solutions labelled with radionuclides we are able to observe such processes directly and - presumably for the first time with due resolution and sensitivity – with our GeoPET method. The same processes are studied with Lattice-Boltzmann flow simulations on µCT-based images of the same samples. This strategy contrasts the common use of computer simulations based on a priori material parameters, and allows for the matching of flow simulation results in “real structures” with real time flow monitoring in the same samples. Here we report on results obtained from a number of drill cores from the ancient Stassfurt salt mine and its overburden, including aged backfill material, which has been analysed in the framework of our joint research project, funded by the Federal Ministry of Education and Research (BMBF) (Wolf et al., 2010).

The superconducting CW- LINAC (1.3 GHz) of the radiation source ELBE is in permanent operation since May 2001/1/. In 2011 an upgrade program of ELBE is in progress to support additional applications. One part of the program is to double the RF-power per cavity to at least 16 kW. Since we started ELBE in May 2001 substantial progress was made in all fields contributing accelerator science. As far as RF-amplifier technology is concerned IOT-based and Solid State Amplifiers compete with klystrons. To prepare for the power upgrade of ELBE we developed a couple of activities, like:

Test of the ELBE RF-couplers and waveguide windows
Test of an available 30 kW IOT amplifier with beam
Test of a 10 kW solid state amplifier (SSPA) with beam
Test of two 10 kW SSPA’ s with beam
Redesign of the Low level RF controller
Redesign of the technical water cooling.

Superlenses create sub-diffraction-limit images by reconstructing the evanescent fields arising from an object. We study the lateral, vertical, and spectral field distribution of three different perovskite-based superlenses by means of scattering-type near-field microscopy. Subdiffraction- limit resolution is observed for all samples with an image contrast depending on losses such as scattering and absorption. For the three lenses superlensing is observed at slightly different frequencies resulting in an overall broad frequency range of 3.6 THz around 20 THz.

A X-ray photoelectron spectroscopy (XPS) of valence band (VB) and core levels are performed for a SiO₂/p-Si heterostructure containing a thin oxide layer of d = 20 nm thickness and implanted by Siþ ions. With an implantation energy of 12 keV the maximum density of the implanted Si⁺ profile is located close to the SiO₂–Si interface at a depth of 18 nm, but a piling-up of Si is also found immediately beneath the surface up to 2 nm, i.e., within the escape depth of XPS electrons. Thus we may expect a partial phase separation associated with Si aggregation and nanocluster formation imbedded in a nonstoichiometric SiO_x matrix. By means of XPS and in comparison to X-ray emission spectroscopy (XES) the related changes of the VB structure are investigated.

Pressurized Thermal Shock (PTS) is identified as one of the safety issues where Computational Fluid Dynamics (CFD) can bring real benefits. Turbulence modeling may impact the overall accuracy of the calculated thermal loads on the Reactor Pressure Vessel (RPV) walls. Therefore advanced methods for turbulent flows are required. In the current paper, we summarize our efforts on large-eddy simulations (LES) of a complex turbulent mixing in the RPV. First, the mesh resolution is investigated, and a comparison procedure is established. The analysis have shown necessity of comparison in both time and frequency domains. Next, a validation against experiment is performed using three cases with different flow rates in the primary loop. The validation results have successfully reproduced the flow patterns and have shown good quantitative agreement for the near-wall temperature drop.

kein Abstract verfügbar

Die Multimodale Bildgebung („Molecular Imaging“) ermöglicht durch die Kombination unterschiedlicher Verfahren eine verbesserte Diagnostik und ist damit Grundlage für eine zielgerichtete personalisierte Therapie von komplexen Krankheiten, wie z. B. Krebs. In diesem Zusammenhang werden insbesondere Computertomographie (CT), Magnetresonanztomographie (MRT), Positronen-Emissions-Tomographie (PET), Single- Photon-Emission-Computed-Tomography (SPECT) und optische Bildgebung eingesetzt [1, 2].
Derivate von 3,7-Diaazabicyclo[3.3.1]nonanen (Bispidine) bieten die Möglichkeit für ein duales Labeling. Sie bilden sehr stabile Komplexe mit radioaktiven Kupferisotopen und gestatten nach entsprechender Funktionalisierung mit Vektormolekülen eine Visualisierung von Tumoren mittels PET [3]. Bispidinliganden verfügen darüber hinaus über weitere funktionelle Gruppen, die die Einführung von Farbstoffen und zielsuchenden Molekülen gestatten.

Die Funktionalisierung der Hydroxygruppe (C9-OH) des Bispidins mit einem Fluoreszenzfarbstoff kann mittels Aktivesterbildung durch Umsetzung mit Chlorameisensäurenitrophenylester und anschießender Urethanbildung mit einem aminofunktionalisierten Farbstoffmolekül realisiert werden.
Es wird über die Synthese derartiger Liganden sowie die Charakterisierung der Fluoreszenzeigenschaften und die Markierung mit dem PET-Radionuklid ⁶⁴ Cu berichtet.

Literatur:

[1] J.V. Frangioni, J. Clin. Oncol. 2008, 26, 4012-4021.
[2] A. Louie, Chem. Rev. 2010, 110, 3146-3195.
[3] S. Juran, M. Walther, H. Stephan, R. Bergmann, J. Steinbach, W. Kraus, F. Emmerling, P. Comba, Bioconjugate Chem. 2009, 20, 347-359.

Because of its chemical similarity and stable tetravalent oxidation state in solution, cerium (Ce) is often employed as an analogue of tetravalent actinides (An(IV)) in various research fields related with actinides. Besides, its dioxide compound, CeIVO₂, has recently attracted considerable attention owing to its wide variety of industrial applications, such as catalysis, oxygen storage, fuel cells, or luminescent materials.
Hydrolysis is one of the most fundamental reactions of metal ions in an aqueous solution. In fact, the hydrolysis behaviour of tetravalent cerium (Ce(IV)) has been studied and often compared with those of An(IV) in order to evaluate its suitability as an analogue of An(IV). Furthermore, the hydrolysis–precipitation process of cerium ions is also of great importance in its industrial applications, since it is one of the most straightforward and simple methods to produce CeO₂. However, despite these importance of hydrolysis reaction in the basic- and applied research fields for Ce, most of the precedent studies have focused on its thermodynamical aspects, and still little has been known about the complex structure of Ce(IV) hydrolytic species formed in solution. In this study, multi-spectroscopic (i.e., X-ray absorption spectroscopy (XAS), high energy X-ray scattering (HEXS), dynamic light scattering (DLS)) and microscopic (TEM) techniques have been employed to structurally characterize the hydrolytic Ce(IV) species in an aqueous solution. The results indicate that nanocrystalline CeO₂ forms and grows up in an aqueous solution as the hydrolysis proceeds with increasing pH. On the presentation, the results will be also discussed with the corresponding An(IV) hydrolytic species.

In the underground rock characterization facility tunnel "ONKALO" in Finland massive biofilms were observed attached to the fractured bedrock at a depth of 70 m. Experiments were performed in the laboratory to study the effect on the behavior of uranium in biofilms by adding uranium to the fracture water with a final uranium concentration (4 x10-5 M) relevant for what can be expected from an injured and leaking waste canister in the far-field during a nuclear event in a HLW repository. The results obtained by analysis, microsensor measurements, TRLFS investigation, EF-TEM/EELS studies and thermodynamic calculations clearly indicate that biofilms have to be considered as microenvironments, which differ significantly from the surrounding medium. Inside the biofilm a pH of 5.37 was recorded, which is about 3.5 units lower than the pH of the surrounding fracture water. Similarly, the redox potential of +73 mV is approximately 420 mV lower than the redox potential measured in the fracture water. The addition of uranium results in an increase of the pH in the biofilm to 7.27 and a decrease of the redox potential to -164 mV mV. The changes of redox potential and pH are influencing the bioavailability of uranium since microbial metabolic processes are sensitive to metals and their speciation. EF-TEM investigations showed that in the biofilm uranium was immobilized intracellular in bacteria by a biologically mediated uranyl phosphate formation similar to needle-shaped Autunite (Ca[UO2]2[PO4]2•2-6H2O) or meta-Autunite (Ca[UO2]2[PO4]2•10-12H2O). In contrast, TRLFS studies of the contaminated fracture water showed aqueous uranium carbonate species, most likely Ca2UO2(CO3)3, which was formed using the available high amount of carbonate from the water. The results are in agreement with the thermodynamic calculation of the theoretical predominance field of uranium species, formed in the uranium contaminated fracture water at the measured geochemical parameters.
Our studies clearly demonstrate that biological systems have to be considered as a part of natural systems in respect to radionuclide immobilization. They are contributing to an improved understanding on the response mechanisms of biofilms towards radionuclides in respect to safety assessments of the radioactive waste repositories.

The redox properties of tetrahalo uranyl(VI) complexes ([UVIO2X4]2 with X = Cl or Br) have been investigated in the ionic liquids [BuMeIm][Tf2N] and [MeBu3N][Tf2N], where [BuMeIm]+ and [MeBu3N]+ are respectively the 1-butyl-3-methylimidazolium and the tributylmethylammonium cations, both associated with the bis(trifluoromethylsulfonyl)imide anion [Tf2N]. The results suggest that the reduction of [UVIO2X4]2 occurs via an Electron transfer – Chemical reaction – Electron transfer mechanism (ECE mechanism). We have shown by voltammetry that the first electron transfer is quasi-reversible and involves one electron, leading to the tetrahalo uranium(V) complex. This compound undergoes a chemical reaction and its stability depends both on the halide ligand and on the ionic liquid. The most stable complex is [UVO2Cl4]3 in [BuMeIm][Tf2N]. We have assumed that the [BuMeIm]+ cation interacts more strongly by H-bonding than the [MeBu3N]+ cation with the uranium complex, as it is the case for other anionic uranium species. Moreover, in presence of excess chloride ions, the consecutive chemical reaction is not observed anymore by cyclic voltammetry.

For the risk assessment of radionuclides in the environment a comprehensive elucidation of the migration behavior of U(VI) in biosphere is necessary. Aim of this study was the quantitative and structural characterization of the interaction between U(VI) and the green alga Chlorella vulgaris at U(VI) concentrations from 5 μM to 1 mM, and in the pH range of 4.4 to 7.0 with special focus on metabolic activity. The obtained findings of the sorption experiments demonstrate clearly, the interactions with U(VI) are heavily influenced by the U(VI) concentration and the status of the Chlorella cells. Living cells bind in a 0.1 mM U(VI) solution at pH 4.4 within 5 min 14.3±5.5 mg U/g dry biomass and dead cells 28.3±0.6 mg U/g dry biomass. Furthermore, Chlorella cells die at concentration higher than 0.1 mM within 48 h. Interestingly, at lower U(VI) concentration of 5 μM, living cells firstly bind almost all U(VI) within the first 5 min of incubation. But then algal cells mobilize up to 80% of the bound U(VI) during ongoing incubation. The release of metabolism related substances is suggested to cause this mobilization of U(VI). As potential leachates for algal-bound U(VI) oxalate, citrate and ATP were tested and found to be able to mobilize more than 50% of the algal-bound U(VI).
The formed U(VI)-algae-complexes were structurally characterized by TRLF, EXAFS and ATR-FTIR spectroscopy. Obtained results demonstrate carboxylic and organic/inorganic phosphate groups were involved in the U(VI) complexation with varying contributions dependent on cell status, U(VI) concentration and pH.
With the help of TEM U(VI) was detected in form of 30-70 nm needle-like deposits in the cell wall of living algae.

The increasing age of European Nuclear Power Plants and envisaged extensions of reactor pressure vessel (RPV) lifetimes up to 80 years require the accurate prediction and management of RPV neutron irradiation embrittlement. LONGLIFE (“Treatment of long term irradiation embrittlement effects in RPV safety assessment”) is a collaborative project of the 7th Framework Programme of EURATOM. This project has been initiated as the next step forward towards obtaining an improved understanding of irradiation effects in RPV steels under conditions representative of long term operation (LTO) of RPVs. Phenomena which might become important at high neutron fluences (such as late-blooming effects and flux effects) must be considered in detail as part of the process of upgrading safety assessments and embrittlement surveillance procedures to underwrite the safety of LTO of RPVs. The work starts with the collection and evaluation of plant-specific information and data such as target neutron fluences for LTO and the chemical compositions of the materials. This includes a survey of available results of RPV materials data from decommissioned plants of validating surveillance data and studying specific irradiation effects relevant for LTO. Microstructural data are obtained from different techniques with the aim of assessing the adequacy of current dose-damage models with respect to their relevance to the mechanisms of irradiation damage associated with LTO of RPVs. Complementary mechanical tests are performed in order to address gaps in existing experimental data. Microstructural data pertaining to the evolution of irradiation damage are correlated with changes in mechanical properties, and the most important influencing factors will be identified. Surveillance guidelines for LTO of RPV base materials and welds will be developed as one of the principal outputs of the project. The scope of work and the project structure are outlined in the paper. Two LTO relevant phenomena – late blooming effect and flux effect – are discussed more detailed.

The present topical review focuses on recent advances in the understanding of the formation of surface nanostructures, an intriguing phenomenon in ion - surface interaction due to the impact of individual ions. In many solid targets, swift heavy ions produce narrow cylindrical tracks accompanied by the formation of a surface nanostructure. More recently, a similar nanometric surface effect has been revealed for the impact of individual, very slow but highlycharged ions. While swift ions transfer their large kinetic energy to the target via ionization and electronic excitation processes (electronic stopping), slow highly-charged ions produce surface structures due to potential energy deposited at the top surface layers. Despite the differences in primary excitation, the similarity between the nanostructures is striking and strongly points to a common mechanism related to the energy transfer from the electronic to the lattice system of the target. A comparison of surface structures induced by swift heavy ions and slow highly-charged ions provides valuable insight to better understand the formation mechanisms.

Es ist kein Abstract vorhanden.

The current paper presents the prediction results of a bubbly flow under plunging jet conditions using multiphase mono- and poly-dispersed approaches. The models consider interfacial momentum transfer terms arising from drag, lift, and turbulent dispersion force for the different bubble sizes. The turbulence is modeled by an extended k–ε model which accounts for bubble induced turbulence. Furthermore in case of a poly-dispersed air–water flow the bubble size distribution, bubble break-up and coalescence processes as well as different gas velocities in dependency on the bubble diameter are taken into account using the Inhomogeneous MUSIG model. This model is a generalized inhomogeneous multiple size group model based on the Eulerian modeling framework which was developed in the framework of a cooperative work between ANSYS-CFX and Forschungszentrum Dresden-Rossendorf (FZD). The latter is now implemented into the CFD code CFX.
According to the correlation on the lateral lift force obtained by Tomiyama (1998); this force changes its sign in dependence on the bubble size. Consequently the entrained small bubbles are trapped below the jet. They can escape from the bubble plume only by turbulent fluctuations or by coalescence. If the size of the bubbles generated by coalescence exceeds the size at which the lift force changes its sign these large bubbles go out from the plume and rise to the surface.
A turbulent model based on an additional source term for turbulence kinetic energy and turbulence eddy dissipation equation is compared to the common concept for modeling the turbulence quantities proposed by Sato et al. (1981). It has been found that the large bubble distribution is slightly affected by the turbulence modeling which affects particularly the bubble coalescence and break-up process.

[Ni(HF₂)(pyz)₂]X {pyz = pyrazine; X = PF₆ ^- (1), SbF₆ ^- (2)} were structurally characterized by synchrotron X-ray powder diffraction and found to possess axially compressed NiN₄F₂ octahedra. At 298 K, 1 is monoclinic (C2/c) with unit cell parameters, a = 9.9481(3), b = 9.9421(3), c = 12.5953(4) angstrom, and beta = 81.610(3) degrees while 2 is tetragonal (P4/nmm) with a = b = 9.9359(3) and c = 6.4471(2) angstrom and is isomorphic with the Cu-analogue. Infinite one-dimensional (1D) Ni-FHF-Ni chains propagate along the c-axis which are linked via mu-pyz bridges in the ab-plane to afford three-dimensional polymeric frameworks with PF₆ ^- and SbF₆ ^- counterions occupying the interior sites. A major difference between 1 and 2 is that the Ni-F-H bonds are bent (similar to 157 degrees) in 1 but are linear in 2. Ligand field calculations (LFT) based on an angular overlap model (AOM), with comparison to the electronic absorption spectra, indicate greater pi-donation of the HF₂ ^- ligand in 1 owing to the bent Ni-F-H bonds. Magnetic susceptibility data for 1 and 2 exhibit broad maxima at 7.4 and 15 K, respectively, and lambda-like peaks in d chi T/dT at 6.2 and 12.2 K that are ascribed to transitions to long-range antiferromagnetic order (T_N). Muon-spin relaxation and specific heat studies confirm these T_N's. A comparative analysis of chi vs T to various 1D Heisenberg/Ising models suggests moderate antiferromagnetic interactions, with the primary interaction strength determined to be 3.05/3.42 K (1) and 5.65/6.37 K (2). However, high critical fields of 19 and 37.4 T obtained from low temperature pulsed-field magnetization data indicate that a single exchange constant (J(1D)) alone is insufficient to explain the data and that residual terms in the spin Hamiltonian, which could include interchain magnetic couplings (J(perpendicular)), as mediated by Ni-pyz-Ni, and single-ion anisotropy (D), must be considered. While it is difficult to draw absolute conclusions regarding the magnitude (and sign) of J(perpendicular) and D based solely on powder data, further support offered by related Ni(II)-pyz compounds and our LFT and density-functional theory (DFT) results lead us to a consistent quasi-1D magnetic description for 1 and 2.

We report on the crystal structure and magnetic behavior of the spin-1/2 compound AgVOAsO₄. Magnetic susceptibility, high-field magnetization, and electron spin resonance measurements identify AgVOAsO₄ as a gapped quantum magnet with a spin gap Delta similar or equal to 13 K and a saturation field mu₀H_s similar or equal to 48.5 T. Extensive band structure calculations establish the microscopic magnetic model of spin chains with alternating exchange couplings J similar or equal to 40 K and J' similar or equal to 26 K. However, the precise evaluation of the spin gap emphasizes the role of interchain couplings which are frustrated due to the peculiar crystal structure of the compound. The unusual spin model and the low energy scale of the exchange couplings make AgVOAsO₄ a promising candidate for an experimental investigation of Bose-Einstein condensation in high magnetic fields.

BiFeO3 thin films have been grown on Pt/Ti/SiO2/Si substrates with pulsed laser deposition using Au as the top electrode. The resistive switching property of the Au/BiFeO3/Pt stack has been significantly improved by carefully tuning the oxygen pressure during the growth, and a large switching ratio of ∼4500 has been achieved. The deposition pressure modifies the concentration of oxygen vacancies and the rectifying behavior of the Au/BiFeO3 junction, and consequently influences the resistive switching behavior of the whole stack. The switching takes place homogeneously over the entire electrode, and shows a long-term retention.

Ultrashort terahertz pulses in the far-infrared spectral region centered around 2 terahertz are used to coherently control an intersubband polarization in a GaAs/AlGaAs quantum well structure at low temperature. While the first pulse excites a macroscopic polarization, a second, temporally delayed pulse switches the polarization off or refreshes it depending on the relative time delay. The switching is directly demonstrated in the time-domain for the few picosecond long free-induction decay of the induced polarization. Additionally, the absorption line is found to be purely homogeneously broadened. Model calculations based on the optical Bloch equations agree well with the experimental data.

Plasmonic properties of self-assembled silver nanoparticles/nanowires array on periodically patterned Si (100) substrate are reported with special attention on the mechanism of nanoparticles self-assembly. The advantage of this bottom up approach over other self-assembling and lithographic methods is the flexibility to tune array periodicity down to 20 nm with interparticle gaps as low as 5 nm along the ripple.
Ripple pattern have shallow modulation (~2 nm) still particles self-assembly was observed in non-shadow deposition. Therefore adatoms diffusion and kinetics is important on ripple surface for the self-assembly. PVD e-beam evaporation method used for deposition has proven to be superior to sputter deposition due to lower incident flux and lower atom energy. It was found that particles self-assembly largely dependent on angle of incidence, substrate temperature, and deposition direction due to ripple asymmetric tilt. Ostwald ripening observed during annealing on ripples substrate has striking dependency on ripple periodicity and was found to be different compared to Ostwald ripening on flat Si surface.
In-situ RBS measurements of deposited silver on flat and rippled substrate confirmed different sticking of atoms on the two surfaces. The difference between maximum and minimum of the calculated local flux show a peak at an incidence angle of 70o with respect to surface normal. This explains the best alignment of particles at this angle of incidence compare to others.
Self-assembled nanoparticles are optically anisotropic, i.e. they exhibit a direction dependent shift in LSPR. The reason of the observed anisotropy is a direction dependent plasmonic coupling. Different in plane and out of the plane dielectric coefficients calculated by modelling Jones matrix elements, confirms that nanoparticle/nanowire array are biaxial anisotropic (ex ¹ ey ¹ ez). The nanoparticles are predominantly insulating while nanowires are both metallic and insulating depending on the dimension.
Silver nanoparticles/nanowires self-aligned on pre-patterned rippled substrate are presented for the first time as an active SERS substrate. Anisotropic SERS response in such arrays is attributed to different field enhancement along and across the ripples. Strong plasmonic coupling in elongated nanoparticles chain results in significantly higher SERS intensity then spherical nanoparticles/nanowires and non-ordered nanoparticles. Higher SERS intensity across the nanowires array in comparison to along the array (bulk silver) confirms electromagnetic field enhancement (hot-junction) is responsible for SERS phenomenon.
Self-assembly of cobalt nanoparticle on ripple pattern substrate is also reported. Due to less adatom mobility and higher sticking cobalt self-assembly is possible only at much higher temperature. A strong uniaxial magnetic anisotropy was observed not observed for non ordered cobalt particles.

Um das Verhalten von Actiniden im Menschen (Stoffwechsel), in geologischen und in biologischen Systemen vorherzusagen, ist es erforderlich deren Speziation genau zu kennen. Zur Bestimmung dieser wird das chemische Verhalten des Urans hinsichtlich Komplexbildungsreaktionen und Redoxreaktionen in Modellsystemen untersucht. Anhand der gewonnenen thermodynamischen Konstanten und dem Redoxverhalten können Risikoabschätzungen für das jeweilige untersuchte System getroffen werden.
Das umweltrelevante Uran(IV)-Uran(VI)-Redoxsystem besitzt mit der metastabilen fünfwertigen Oxidationsstufe einen zumeist kurzlebigen Zwischenzustand. Innerhalb dieser Arbeit gelang es erstmalig die Uran(V)-Fluoreszenz mittels laserspektroskopischer Methoden nach zu weisen. Beispielsweise konnte das Bandenmaximum von aquatischem Uranyl(V) im perchlorhaltigem Medium (λex = 255 nm) mit 440 nm, bei einer Fluoreszenzlebensdauer von 1,10 ± 0,02 μs bestimmt werden. Die fluoreszenzspektroskopische Untersuchung eines aquatischen [U(V)O2(CO3)3]5--Komplexes (λex= 255 nm und 408 nm) zeigte bei Raumtemperatur keine Fluoreszenz.
Durch Anwendung der Tieftemperaturtechnik wurden bekannte Quencheffekte des Carbonats unterdrückt, so dass bei beiden Anregungswellenlängen ein für Uran(V) typisches Fluoreszenzspektrum im Bereich von 375 nm bis 450 nm, mit Bandenmaxima bei 401,5 nm (λex = 255 nm) und 413,0 nm (λex = 408 nm) detektiert werden konnte. Darüber hinaus konnte bei 153 K (λex = 255 nm) eine Fluoreszenzlebensdauer von 120 ± 0,1 μs bestimmt werden. Untersetzt wurden diese fluoreszenzspektroskopischen Nachweise durch mikroskopische Studien verschiedener Uran(IV)-Festphasen (Uraninit…UO2, Uran(IV)-Tetrachlorid…UCl4) und einer sulfathaltigen Uran(IV)-Lösung (UIVSO4). Diese wurden durch kontinuierliche Sauerstoffzufuhr zu Uran(VI) oxidiert. Die ablaufende Oxidation wurde mit dem konfokalen Laser Scanning Mikroskop (CLSM) verfolgt, wobei die Proben mit einer Wellenlänge von 408 nm zur Fluoreszenz angeregt wurden. Die auftretenden Bandenmaxima bei 445,5 nm (UO2), bei 445,5 nm (UCl4) und bei 440,0 nm (UIVSO4) konnten eindeutig der Uran(V)-Fluoreszenz zugeordnet werden.
Zur Bestimmung thermodynamischer Konstanten mit Hilfe der Tieftemperaturfluoreszenz wurde zunächst der Einfluss der Temperatur auf das Fluoreszenzverhalten des freien Uranyl(VI)-Ions näher betrachtet. Es zeigte sich, dass mit Erwärmung der Probe (T>298 K) die Fluoreszenzlebensdauer von 1,88 μs (298 K) deutlich absinkt. Die Fluoreszenzintensität verringerte sich dabei um 2,3 % pro 1 K zwischen 273 K und 313 K. Im Gegensatz dazu, steigt die Fluoreszenzlebensdauer um das 150-fache auf 257,9 μs bei einer Verminderung der Temperatur (T <298 K) auf 153 K. Das weitere Absenken der Temperatur (T <153 K) zeigte keinen Einfluss auf die Fluoreszenzlebensdauer. Die Lage der Hauptemissionsbanden des freien Uranyl(VI)-Ions (488,0 nm, 509,4 nm, 532,4 nm, 558,0 nm, 586,0 nm) zeigte bei diesen Untersuchungen keine temperaturabhängige Verschiebung.
Die Validierung der Tieftemperaturtechnik zur Bestimmung thermodynamischer Konstanten mittels zeitaufgelöster laserinduzierten Fluoreszenzspektroskopie erfolgte anhand des Uran(VI)-Citrat-Systems. Im Gegensatz zu bisherigen fluoreszenzspektroskopischen Betrachtungen bei Raumtemperatur wurde das Fluoreszenzsignal bei tiefen Temperaturen mit einsetzender Komplexierung nicht gequencht, woraus die Ausprägung einer gut interpretierbaren Fluoreszenz resultierte. Die Analyse der spektralen Daten mit SPECFIT ergaben mit log β 101 = 7,24 ± 0,16 für den [UO2(Cit)]--Komplex und log β 202 = 18,90 ± 0,26 für den [(UO2)2(Cit)2]2--Komplex exakt die in der Literatur angegebenen Stabilitätskonstanten. Zudem konnten Einzelkomponentenspektren mit Bandenmaxima bei 475,3 nm, 591,8 nm, 513,5 nm, 537,0 nm und 561,9 nm für den 1:0:1-Komplex und 483,6 nm, 502,7 nm, 524,5 nm, 548,1 nm und 574,0 nm für den 2:0:2-Komplex und Fluoreszenzlebensdauern von 79 ± 15 μs (1:0:1) und 10 ± 3 μs (2:0:2) bestimmt werden.
Zur Modellkomplexierung des Uran-Citrat-Systems wurde in dieser Arbeit auch das Komplexbildungsverhalten von U(IV) in Gegenwart von Citronensäure untersucht. Hierbei wurden über den gesamten pH-Wertbereich gelöste Uran-Citrat-Spezies spektroskopisch nachgewiesen und die Stabilitätskonstanten sowie die Einzelkomponentenspektren für die neu gebildeten Uran(IV) und (VI)-Spezies bestimmt. Für die neu gebildeten Citrat-Komplexe des sechswertigen Urans wurden Komplexbildungskonstanten von log β 203 = 22,67 ± 0,34 ([(UO2)2(Cit)3]5-) und log β 103 = 12,35 ± 0,22 ([UO2(Cit)3]7-) und für die Komplexe des vierwertigen Urans von log β 1-21 = -9,74 ± 0,23 ([U(OH)2Cit]-) und log β 1-31 = -20,36 ± 0,22 ([U(OH)3Cit]2-) bestimmt.
Untersuchungen zum Redoxverhalten von Uran in Gegenwart von Citronensäure zeigten unter aeroben und anaeroben Versuchsbedingungen eine photochemische Reduktion vom U(VI) zu U(IV), welche spektroskopisch nachgewiesen werden konnte. Dabei zeigt speziell die Reaktion unter oxidierenden Bedingungen, welchen großen Einfluss vor allem organischen Liganden auf das chemische Verhalten des Urans haben können. Sowohl die Reduktion unter O2- als auch die unter N2-Atmosphäre, weisen ein Maximum bei einem pH-Wert von 3,5 bis 4 auf. Unter anaeroben Bedingungen reduziert die Citronensäure mit ca. 66 %, 14 % mehr Uran(VI) zu Uran(IV) als unter anaeroben Bedingungen mit ca. 52 %.
Ab einem pH-Wert von 7 konnte eine Reduktion nur unter sauerstofffreien Bedingungen festgestellt werden.
Die Wechselwirkung von U(VI) in Gegenwart von Glucose wurde hinsichtlich Reduktion und Komplexierung des Uran(VI) betrachtet. Mit Hilfe der zeitaufgelösten laserinduzierten Fluoreszenzspektroskopie bei tiefen Temperaturen wurde dabei ein Uranyl(VI)-Glucose-Komplex nachgewiesen. Die Komplexierung wurde lediglich bei pH 5 beobachtet und weist eine Komplexbildungskonstante von log β I=0,1 M = 15,25 ± 0,96 für den [UO2(C6H12O6)]2+-Komplex auf. Mit einer Fluoreszenzlebensdauer von 20,9 ± 2,9 μs und den Hauptemissionsbanden bei 499,0nm, 512,1 nm, 525,2 nm, 541,7 nm und 559,3 nm konnte der Uranyl(VI)-Glucose-Komplex fluoreszenzspektroskopisch charakterisiert werden. Unter reduzierenden Bedingungen wurde, ab pH-Wert 4 eine auftretende Umwandlung vom sechswertigen zum vierwertigen Uran durch Glucose in Gegenwart von Licht beobachtet. Der Anteil an gebildetem Uran(IV) steigt asymptotischen bis zu einem pH-Wert von 9, wo das Maximum mit 16 % bestimmt wurde. Als Reaktionsprodukt der Redoxreaktion wurde eine Uran(VI)-Uran(IV)-Mischphase mit der Summenformel [UIV(UVIO2)5(OH)2]12+ identifiziert.
Mit Hilfe der cryo-TRLFS wurde, durch Verminderung von Quencheffekten die Uranspeziation in natürlichen Medien (Urin, Mineralwasser) direkt bestimmt. Proben mit Uran-Konzentrationen von < 0,1 μg/L konnten dadurch analysiert werden. In handelsüblichen Mineralwässern wurde die zu erwartende Komplexierung durch Carbonat nachgewiesen. Im Urin zeigte sich in Abhängigkeit vom pH-Wert eine unterschiedliche Uranspeziation. Die fluoreszenzspektroskopische Untersuchung wies bei niedrigerem pH-Wert (pH<6) eine Mischung aus Citrat- und Phosphat-Komplexierung des U(VI) und bei höheren pH-Wert (pH>6) eine deutliche Beteilung von Carbonat an der Komplexierung auf. Diese Ergebnisse stehen in sehr guter Übereinstimmung mit theoretischen Modellrechnungen zur Uranspeziation im Urin.
Die in dieser Arbeit gewonnenen Ergebnisse zeigen, dass für eine zuverlässigere Prognose des Urantransportes in Geo- und Biosphäre in Zukunft nicht nur Betrachtungen zur Komplexchemie, sondern auch zum Redoxverhalten des Urans nötig sind, um die Mobilität in der Natur richtig abschätzen zu können.

The Institute of Ion Beam Physics and Materials Research (IIM) is one of the six institutes of what was called Forschungszentrum Dresden-Rossendorf (FZD) until the end of 2010, but since this year 2011 is called “Helmholtz-Zentrum Dresden-Rossendorf (HZDR)”. This change reflects a significant transition for us: it means that the research center is now member of the Helmholtz Association of German Research Centers (HGF), i.e., a real government research laboratory, with the mission to perform research to solve fundamental societal problems. Often to date those are called the “Grand Challenges” and comprise issues such as energy supply and resources, health in relation to aging population, future mobility, or the information society.
This Annual Report already bears the new corporate design, adequate for the time of its issueing, but reports results from the year 2010, when we were still member of the Leibniz Association (WGL). Our research is still mainly in the fields of semiconductor physics and materials science using ion beams. The institute operates a national and international Ion Beam Center, which, in addition to its own scientific activities, makes available fast ion technologies to universities, other research institutes, and industry. Parts of its activities are also dedicated to exploit the infrared/THz freeelectron laser at the 40 MeV superconducting electron accelerator ELBE for condensed matter research. For both facilities the institute holds EU grants for funding access of external users.

At the beginning of 2011, the former Forschungszentrum Dresden-Rossendorf (FZD) was fully integrated into the Helmholtz Association, as Helmholtz-Zentrum Dresden-Rossendorf (HZDR). Therefore, the present Annual Report 2010 of the Institute of Radiochemistry (IRC) is published as the first HZDR-Report.

The Institute of Radiochemistry is one of the six Research Institutes of this centre. IRC contributes to the research program “Nuclear Safety Research” in the “Research Field of Energy” and performs basic and applied research in radiochemistry and radioecology. Motivation and background of our research are environmental processes relevant for the installation of nuclear waste repositories, for remediation of uranium mining and milling sites, and for radioactive contaminations caused by nuclear accidents and fallout. Because of their high radiotoxicity and long half-life the actinides are of special interest.

The first international round-robin exercise for the measurement of the long-lived radionuclide ¹⁰Be has been conducted. Ten participating accelerator mass spectrometry (AMS) facilities have each measured three samples at the 10^-12-10^{-14 10}Be/⁹Be level. All results have been made traceable to the NIST SRM 4325 standard to avoid additional discrepancies that arise when different facilities use different calibration materials. Hence, the data concentrates on pure measurement distinctions. Multivariate statistical investigations have been performed to reveal a bias between facilities, i.e. two distinguished groups could be identified. Maximum discrepancies between two single facilities are in the range of 6-31% depending on the absolute ¹⁰Be/⁹Be value. These findings should be considered when comparing ¹⁰Be data produced at one AMS facility with that produced at another facility, which is e.g. often the case for in-situ ¹⁰Be dating studies. Round-robin exercises are a very helpful tool as part of an overall quality assurance scheme to improve the accuracy, and not only the precision, of AMS data.

The incorporation of transition metal dopants in semiconductors above their solubility limit is the main challenge for the fabrication of diluted ferromagnetic semiconductors. Low temperature molecular beam epitaxy (LT-MBE) is the standard technique for the fabrication of GaAs:Mn. For Ge:Mn the LT-MBE approach seems to be successful to grow Mn rich clusters or nanowires [1]. Nevertheless, hysteretic magnetotransport properties were not observed in such Ge:Mn nanostructures. On the other hand, pulsed laser annealing is a successful annealing method far from thermodynamic equilibrium and a promising technique for the fabrication of ferromagnetic Ge:Mn [2] and for III-V semiconductors [3]. In this work, Mn has been implanted into nearly intrinsic n-Ge substrates up to a depth of around 100 nm at low temperatures and annealed by pulsed laser annealing. We observed the same hysteretic properties up to 30 K via SQUID magnetization as well as via magnetotransport measurements. Furthermore, Ge:Mn films show a spontaneous magnetization in field-cooled SQUID measurements below 250 K. Segregated secondary phases with a regular distance slightly above 50 nm have been detected by HRTEM measurements near the sample surface. At elevated temperatures the confirmation of similar magnetization and magnetotransport properties of the p-Ge:Mn surface layer is hampered by the significant contribution of the underlying n-Ge substrate to the conductivity. Further experiments with insulating substrates and proper etching methods are necessary to clarify the ferromagnetic contribution of each individual layer.

[1] M. Jamet et al., Nature. Mat. 5, 653 (2006)
[2] Shengqiang Zhou et al., Phys. Rev. B 81, 165204 (2010)
[3] M. A. Scarpulla et al., Appl. Phys. Lett. 82, 1251 (2003)

The incorporation of transition metals dopants in semiconductors over their solubility limit is the main challenge for the fabrication of diluted ferromagnetic semiconductors. Low temperature molecular beam epitaxy (LT-MBE) is the standard technique for the fabrication of GaAs:Mn. Nevertheless, for Ge:Mn [1] the LT-MBE approach seems to be not successful to reach hole concentrations necessary for hole mediated ferromagnetism. On the other hand, pulsed laser annealing is a successful nonequilibrium annealing method and a promising technique for the fabrication of diluted Ge:Mn [2] and for III-V semiconductors, e.g. GaAs:Mn [3]. Recently we fabricated a ca. 100 nm thick Ge:Mn film by low temperature Mn-implantation followed by pulsed laser annealing and observed hole-mediated ferromagnetism up to 30 K via SQUID magnetization as well as magnetotransport measurements. The anisotropy of ferromagnetic Ge:Mn films will be discussed. Moreover, the Ge:Mn films show a remanent magnetization up to 220 K which is lower than the Curie temperature of typical Mn_xGe_y clusters [1]. The confirmation of spin-polarized hole transport up to 220 K becomes difficult because at elevated temperatures the conductivity is mainly determined by the Ge substrate.
[1] M. Jamet et al., Nature. Mat. 5, 653 (2006)
[2] Shengqiang Zhou et al., PRB 81, 165204 (2010)
[3] Danilo Bürger et al., PRB 81, 115202 (2010

Ferromagnetic Ge:Mn has been fabricated by Mn implantation in intrinsic Ge wafers and by pulsed laser annealing with a pulse duration of 300 ns. Due to a segregation instability during laser annealing, Mn segregates at the liquid-solid interface and an approximately 40 nm thick Ge:Mn surface layer is strongly enriched with Mn. Plan-view images reveal a percolating Mn-rich nanonet. Hysteretic anomalous Hall effect has been observed up to 30 K, but it vanishes after etching away the 40 nm thick Mn-rich Ge:Mn surface layer. The nanonet seems to support the correlation between magnetization and hysteretic Hall resistance. Intrinsic scattering in the threads or vertices of this nanonet may lead to the observed anomalous Hall effect.

Vector-magneto-optical generalized ellipsometry (VMOGE) allows to perform generalized Mueller matrix ellipsometry in a magnetic field of arbitrary orientation and magnitude up to 0.4 T at room temperature. We measured the magneto-optical properties of Fe, Co, and Ni thin films on ZnO substrates and extracted the wavelength dependent magneto-optical dielectric tensor together with the coupling constant Q under saturation magnetization conditions via model analysis. We converted our magneto-optical dielectric tensor of Fe, Co, and Ni into the optical conductivity tensor and the results agreed well with the literature experimental values.

Design and optimization of separation units, e. g., distillation and absorption columns with flow distribution packings, require detailed knowledge about the internal flow conditions and their impact on the process behavior. This in turn calls for suitable measuring techniques, which can give a detailed insight into such devices, especially for studies on a laboratory and pilot scale. Traditional instrumentation, such as compartment-type liquid collectors installed below packings, or distributed temperature, pressure and conductivity probes, often falls too short if detailed knowledge on flow conditions is required. This concerns especially local liquid holdup, liquid maldistribution, liquid films thickness, wetting of the packing surface, or bubble size and droplet distribution at trays. Advanced imaging techniques, such as tomography, have found only marginal attention in investigations of separation columns with structured and modern dumped flow distribution packings, mostly due to limited spatial and temporal resolution but also due to prevailing technological problems encountered in such applications. In this study, the potentials and limits of some of the most recently emerged tomographic imaging modalities for multiphase flows have been investigated and reviewed, i.e., ultra-fast X-ray tomography, high-resolution gamma-ray tomography, wire-mesh sensor techniques, and X-ray microtomography with respect to a possible application in separation columns with flow distribution packings.

The structure of glycyl-L-glutamyl-L-phosphoseryl-L-leucine, (C16H29N4O11P)2.3H2O, has monoclinic (P21) symmetry. The dimeric structure is characterized by an unusual non-head-to-tail arrangement based on an extended intermolecular hydrogen bonding network. Two of the three H2O molecules included in the network are disordered. The protonation constants of the tetrapeptide were determined as log K1 = 1.50, log K2 =3.63, log K3 =4.32, log K4 =6.08 and log K5 =8.65 by potentiometric pH titration.

In this study structural and magnetic character of the expanded austenite phase (γN) layer formed on a medical grade CoCrMo alloy by a low-pressure Radio-Frequency plasma nitriding process was investigated. The formation of the expanded austenite phase is facilitated at a substrate temperature near 400 °C for 1, 2, 4, 6 and 20 h under a gas mixture of 60% N2–40% H2. The magnetic state of the γN layers was determined by a surface sensitive technique, magneto-optic Kerr effect (MOKE), and with a scanning probe microscope in magnetic force mode (MFM). Strong evidence for the ferromagnetic nature of the γN-(Co,Cr,Mo) phase is provided by the observation of stripe domain structures and the hysteresis loops. The ferromagnetic state for the γN phase observed here ismainly linked to large lattice expansions (~10%) due to high N contents (~30 at.%). As an interstitial impurity, nitrogen dilates the host lattice i.e. the Co–Co (or Fe–Fe) distance is increased, which strongly influences the magnetic interactions. An analogy between the magnetic properties of the expanded phases, γN-(Fe,Cr,Ni) and γN-(Co,Cr,Mo), formed in austenitic stainless steel alloys and the CoCrMo alloy of this study is made, and it is suggested that the ferromagnetic states for the γN-(Co,Cr,Mo) and γN-(Fe,Cr,Ni) phases may be correlated with the volume dependence of the magnetic properties of fcc-Co/Co4N and fcc-Fe/Fe4N, respectively.

Ion erosion as a tool for nanostructuring has proven its versatility with respect to surface morphology modifications. Ion irradiation parameters, e.g. ion energy, fluence, incident angle, and sample temperature, can be varied in order to assemble self-organized periodically ordered arrays of nano-dots and ripples. Particularly, nanopatterning of magnetic materials is meaningful because not only the surface morphology is affected, but the overall magnetic properties are accordingly modified. Here we present a novel bottom-up method of magnetic film patterning, where ordered periodic MgO ripple surfaces with a wavelength on the nanometer scale, ion sculptured along a few arbitrary in-plane orientations and outstandingly fully crystalline upon ion irradiation, are coated by a magnetic Fe layer. Due to a cubic symmetry of Fe an in-plane fourfold magnetic anisotropy is induced and in addition, an uniaxial magnetic anisotropy arises due to the surface morphology. The uniaxial magnetic anisotropy orientation and strength is controlled by an arbitrarily chosen irradiation direction with respect to the sample plane and the ripple wavelength is set by the ion energy, respectively. Thus an ensemble of twofold and fourfold anisotropy is created and analyzed by ferromagnetic resonance, magnetooptic Kerr effect, and X-ray diffraction techniques. Theoretical analysis reveals both the anisotropy fields and their directions that are in agreement with the experiment. This work is supported by DFG FA314/6-1.

Ion erosion of MgO substrates produces highly ordered surface patterns. The so-called ripples are not only induced along any arbitrary in-plane orientation but outstandingly, they stay crystalline upon ion irradiation. Due to the low lattice mismatch single crystalline Fe films can be grown onto these periodically modulated MgO(100) templates. Despite the intrinsic magnetic property of bcc Fe, i.e. cubic anisotropy, an additional ripple morphology driven uniaxial magnetic anisotropy is introduced. Thus an ensemble of twofold and fourfold symmetry is created, which is confirmed by ferromagnetic resonance and magneto-optic Kerr effect measurements. The orientation and strength of the uniaxial anisotropy, which mainly originates from shape and step-edge contributions, depends on the angle of the ripple ridges elongation with regard to the [100] direction of MgO and on the Fe film thickness, respectively. Theoretical analysis reveals anisotropy fields and orientations of both anisotropy contributions that are in agreement with the experiment.

Previously postulated from laboratory studies, the occurrence of antimony-sulfur species in geothermal waters could now be proven using anion-exchange chromatography-inductively coupled plasma-mass spectrometry. The two thioantimony species detected by AEC-ICP-MS in oxic synthetic antimonite-sulfide solutions were assigned to tri- and tetrathioantimonate based on their S/Sb ratios and structural characterization by X-ray absorption spectroscopy (XAS). XAS confirmed that the initial species formed under anoxic conditions from antimonite at a 10-fold sulfide excess is trithioantimonite. Trithioantimonite rapidly transforms to tetrathioantimonate in the presence of oxygen or to antimonite at excess OH(-) versus SH(-) concentrations, and escapes chromatographic detection. In natural geothermal waters, up to 30% trithioantimonate and 9% tetrathioantimonate were detected. Their occurrence increased at increasingly alkaline pH and with increasing sulfide and decreasing oxygen conce!
ntrations. Considering the large sulfide excess (100 to 10 000-fold) the proportion of thioantimonates formed under natural conditions is lower than expected from synthetic solutions. Together with the observed high thioarsenate concentrations (>80% of total arsenic), this indicates that in direct competition with arsenic for a limited source of sulfide, thioantimonates form less spontaneously than thioarsenates. Interactions of arsenic and antimony with sulfur can therefore be decisive for similarities or differences in their environmental behavior.

Heterogeneous TiO(2) films with nanocrystalline (nc-) rutile and amorphous (a-) phases were annealed in vacuum up to 450 degrees C. The structural and morphological changes were studied by in situ X-ray absorption and ex-situ X-ray diffraction and atomic force microscopy. The annealing process leads to phase and morphological changes depending on the initial phase mixture. Films with dominant nc-rutile phase are quite stable whereas in a-TiO(2)-containing films the a-TiO(2) regions crystallize into nc-anatase at 300 degrees C. The latter is attributed to the initial anatase-like character of a-TiO(2). Interestingly, at 450 degrees C nc-anatase or nc-rutile is preferentially promoted for high or low initial a-TiO(2) contents, respectively.

Reactive pulsed magnetron sputtering (RPMS) using high metal to oxygen flux ratio is know to provide high-quality transparent and electrically conductive Al-doped ZnO (AZO) films at low temperatures (Ts<200 °C) [1]. However, in this case electrical properties of AZO films strongly depend on deposition temperature and the films even turn insulating at Ts>350 °C [2]. It has been shown that energy deposition during growth due to the elevated TS and from the flux of energetic particles incident on the substrate causes preferential Zn desorption. This leads to a higher Al concentration in the films, which exceeds the solubility limit and triggers the formation of an insulating metastable homologous (ZnO)3Al2O3 phase. This phase impedes crystal growth (decreasing the grain size) and causes a significant increase of free electron scattering which leads to observed increase of the film electrical resistivity [2]. Little is known about effect of this phase formation on the AZO film optical properties, although it is of special importance for understanding of the influence of the secondary phase formation on the fundamental and above-band gap band-to-band electron transitions in this material.

In order to clarify the problem the films with defined Al concentrations (0-20 at.%) grown by RPMS at temperatures ranging from RT to 550 °C were investigated. They were characterized by Hall-effect measurements, spectroscopic ellipsometry and Raman spectroscopy. These results were complemented by the Rutherford back scattering, elastic recoil detection analysis, X-ray diffraction and X-ray absorption near edge structure (XANES) measurements.

The comparison of undoped ZnO and AZO films with the highest crystallinity shows that an incorporation of ~1 at.% of Al leads to the best electrical properties, although (ZnO)3Al2O3 phase signature appears in its Al K-edge XANES spectra even at this low dopant concentration. This is accompanied by the broadening of the allowed ZnO Raman lines and appearance of the broad band around 565 cm-1 which is interpreted as a defect-enhanced A1 LO mode. Increase of Al concentration up to 8-10 at.% leads to deterioration of the film electrical properties accompanied by an increase of the (ZnO)3Al2O3 phase-related peaks in Al K-edge spectra. At this level of doping the allowed ZnO Raman lines are no longer detectable, but the defect-induced Raman features change their intensity distribution. Finally, increasing cFAl>10 at.% leads to formation of electrically insulating nanocrystalline films, which show even more intense (ZnO)3Al2O3 phase-related XANES peaks. The band gap of these films is significantly broader compared to that of undoped ZnO or conductive AZO layers. The latter may be understood in analogy to optical properties of the metastable wurtzite MgxZn(1-x)O alloys.

[1] B. Szyszka, Thin Solid Films 351, 164 (1999)
[2] M. Vinnichenko et al, Appl. Phys. Lett. 96, 141907 (2010).

Ultrasound and magnetization studies of bond-frustrated ZnCr₂S₄ spinel are performed in static magnetic fields up to 18 T and in pulsed fields up to 62 T. At temperatures below the antiferromagnetic transition at T_N1 ≈ 4 K, the sound velocity as a function of the magnetic field reveals a sequence of steps followed by plateaus indicating a succession of crystallographic structures with constant stiffness. At the same time, the magnetization evolves continuously with a field up to full magnetic polarization without any plateaus in contrast to geometrically frustrated chromium oxide spinels. The observed high-field magnetostructural states are discussed within a H-T phase diagram taking into account the field and temperature evolution of three coexisting spin structures and subsequent lattice transformation induced by the magnetic field.

We have investigated low-temperature elastic properties of PrMg₃ with a non-Kramers Γ₃ doublet ground state by using ultrasonic measurements under high field up to 18 T down to 20 mK. A softening of the elastic constant (C₁₁−C₁₂)/2 has been observed below 8 K due to the non-magnetic Γ₃ doublet possessing electric quadrupole O_u and O_v with Γ₃ symmetry and magnetic octupole T_xyz with Γ₂. This result appreciably is deviated from a theoretical fitting of the quadrupole susceptibility based on the crystal-electric-field levels below 800 mK. Furthermore, the (C₁₁−C₁₂)/2 shows strange magnetic dependence up to 18 T below 1.7 K, which are inconsistent with the theoretical results

We report measurements of the temperature dependence of the radio frequency magnetic penetration depth in Ba_0.68K_0.32Fe₂As₂ and Ba(Fe_0.93Co_0.07)₂As₂ single crystals in pulsed magnetic fields up to 60 T. From our data, we construct an H–T-phase diagram for the interplane (H || c) and in-plane (H || ab) directions for both compounds. For both field orientations in Ba_0.68K_0.32Fe₂As₂ we find a concave curvature of the H_c2(T) lines with decreasing anisotropy and saturation towards lower temperature. Taking into account Pauli spin paramagnetism we can describe H_c2(T) and its anisotropy. In contrast, we find that Pauli paramagnetic pair breaking is not essential for Ba(Fe_0.93Co_0.07)₂As₂. For this electron-doped compound, the data support a H_c2(T) dependence that can be described by the Werthamer–Helfand–Hohenberg model for H || ab and a two-gap behavior for H || c.

We report the results of high-resolution neutron powder diffraction studies of Fe_xO (x = 0.925, 0.94) in the vicinity of the low-temperature antiferromagnetic transition and at pressures up to 8 GPa. Our analysis shows that the P-T phase diagram of Fe_xO is strongly affected by the composition and defect structure of the material. We observe the divergence of critical temperatures of magnetic and structural transitions. In contrast to the stoichiometric antiferromagnet MnO, we find no correlation between the magnitude of the magnetic moment of iron and the degree of the rhombohedral distortion in Fe_xO. We suggest that the defect structure of antiferromagnetic Fe_xO significantly influences the temperature of the structural transition.

The magnetization of a Ho₂Fe₁₇ single crystal has been measured along the principal crystallographic directions in pulsed magnetic fields up to 60 T. Stepwise discontinuities in the magnetization occur at 45 and 55 T along the [120] and [100] directions, respectively. The data allowed us to deduce the molecular field at the Ho site. As a cross check, the molecular field was determined as well from a magnetization measurement when the Ho₂Fe₁₇ single crystal was let rotate freely. Both values are in good agreement with each other.

Fragestellung: Die klassischen Protonenbeschleuniger liefern einige Nanosekunden lange Pulse mit hoher Wiederholfrequenz im Megahertzbereich. Mit der neuartigen Technologie der Laser Beschleunigung werden hingegen kürzere, nur einige Pikosekunden lange Teilchenpakete mit wesentlich geringerer Pulsfrequenz von einigen Hertz bei gleichzeitig viel höherer Pulsintensität erzeugt. Vor einem Einsatz der Laserbeschleunigung in der Strahlentherapie muss die möglicherweise abweichende biologische Wirksamkeit, sei es durch die andere Zeitstruktur oder durch die höhere Pulsdosisleistung, gegenüber den klassischen Teilchenstrahlen untersucht werden. Im Beitrag wird der Stand der neuen Technologie im Hinblick auf eine Protonentherapie diskutiert und die weltweit ersten systematischen Zellbestrahlungen mit Bestimmung von Dosis-Effekt-Kurven für Laser beschleunigte Protonen vorgestellt.
Methodik: Wichtige Voraussetzungen für die Nutzung Laser beschleunigter Teilchen in der klinischen Therapie oder auch für strahlenbiologische Experimente sind die Anpassung des Lasersystems, sowie der Aufbau einer geeigneten Strahlführung und eines Dosimetriesystems. Die Zellbestrahlungen wurden am 150-Terrawatt-Lasersystem DRACO im Helmoltz-Zentrum Dresden-Rossendorf durchgeführt. Die Protonenpulse haben eine Länge von ca. 1 ps und eine Wiederholrate von 0,2 Hz. In einer ersten Serie von in-vitro Zellbestrahlungen mit Strahlendosen im Bereich von 0,3 bis 4 Gy wurde der Anteil der überlebenden Zellen und die 24 h nach Bestrahlung verbliebenen DNA-Doppelstrangbrüche für die Tumor-Zelllinie SKX bestimmt. Zusätzlich wurden Referenzbestrahlungen an einem Tandembeschleuniger mit kontinuierlichen Protonenstrahlen und einer 200 kV-Röntgenröhre durchgeführt.
Ergebnisse: Die neue Technologie bietet ein hohes Potenzial zur Verbesserung der Strahlentherapie mit Protonen. Insbesondere sind kleine, preiswerte Anlagen denkbar, die in bestehende Kliniken integriert werden können. Die präzise dosimetrische Erfassung Laser beschleunigter Strahlen ist möglich. Die biologische Wirksamkeit zwischen konventionell und Laser beschleunigten Protonen zeigt in Zellbestrahlungen keinen signifikanten Unterschied.
Schlussfolgerung: Die ersten Schritte zur Entwicklung einer neuen, auf Hochintensitätslasern basierenden Protonentherapieanlage sind erfolgreich durchgeführt worden. Weitere Untersuchungen zur biologischen Wirksamkeit am Tiermodell müssen erfolgen. Ausserdem sind weitere Entwicklungen und Verbesserungen der Laser Beschleuniger notwendig, damit ein klinischer Einsatz möglich wird.
Die Arbeit wird gefördert durch das BMBF 03ZIK445.

The design of future spintronic devices requires a quantitative understanding of the microscopic linear and nonlinear spin relaxation processes governing the magnetization reversal in nanometer-scale ferromagnetic systems. Ferromagnetic resonance is the method of choice for a quantitative analysis of relaxation rates, magnetic anisotropy and susceptibility in a single experiment. The approach offers the possibility of coherent control and manipulation of nanoscaled structures by microwave irradiation. Here, we analyze the different excitation modes in a single nanometer-sized ferromagnetic stripe. Measurements are performed using a microresonator set-up which offers a sensitivity to quantitatively analyze the dynamic and static magnetic properties of single nanomagnets with volumes of (100 nm)(3). Uniform as well as non-uniform volume modes of the spin wave excitation spectrum are identified and found to be in excellent agreement with the results of micromagnetic simulations which allow the visualization of the spatial distribution of these modes in the nanostructures.

Current work at HZDR will be presented with special emphasis on the development strategy for the DYN3D code as a main component of a diverse 3D coupled core simulation tool for fast reactors and on the work on designable feedback coefficients for sodium cooled fast reactors.
DYN3D is a code for steady-state and transient analysis, currently updated for the use for fast reactors. The code has been extended to multi-group use as well as to the solution of the SP3 equations on rectangular and recently to triangular grid. First verification results for the new triangular multi-group solver will be presented and compared to a HELIOS reference solution. The thermal hydraulics of the code has already been updated with the sodium properties for the steady state and transient core simulation. In an industry funded project the fuel rod modeling will be improved by coupling with a fuel rod analysis code and by extension of the model to consider fuel rod expansion. First full core tests for SFR will be performed within ESFR. LFR validation will be performed on the Guinevere experiments at Mol/Belgium in the project FREYA. Validation of the code for SFR is foreseen in a cooperation project with the IPPE in Obninsk/Russia, already under negotiation. After these validation projects, DYN3D will be a diverse, well validated 3D nodal code for fast reactor steady state and transient analysis.
The new idea of improving the safety coefficients by the insertion of moderating material will be presented. The effect of moderating material on the sodium void effect, the neutron spectrum, and the kinf is investigated. The use of a zirconium hydride ZrH moderator improves the fuel temperature effect, the coolant effect of the system and the sodium void effect significantly. All changes lead to a significant increase in stability of the fast reactor against transients. The effect of different spatial arrangements of the moderating material is investigated. It is demonstrated, that the insertion of the moderating material does not have a significant influence on the fuel element power and burnup distribution. The use of fine distributed moderating material creates a new degree of freedom in the design of sodium cooled fast reactors without implying constraints on the core and the fuel element design. It opens the way to create designable feedback effects in a fast reactor core to optimize the response of the reactor core to transients and incidents. The moderating material has only a small influence on the breeding effect and the MA production.

Laterally patterned magnetic hybrid structures display novel magnetic reversal properties, which are related to the fundamental exchange coupling between material interfaces. We present an analytical model that depicts the influence of dipolar fields inmesoscopic structureswith modulated saturationmagnetization on the magnetization reversal and the local magnetic states, as well as the occurrence of a lateral exchange-spring effect. This is done by confining a lateral array of stripes with alternating saturation magnetizationMS in a micrometer-sized square, introducing external boundary conditions to the system. The calculations were performed for distinct stripe and array sizes, as well as different MS values. From the calculations a stability region of array and stripe sizes is derived, in which the lateral exchange-spring effect occurs. The obtained modeling results were found to be in agreement with the experimental data. The model adds a building block to the fundamental understanding of magnetic hybrid structures.

Shear and bulk viscosities of deconfined gluonic matter are investigated within an effective kinetic theory by describing the strongly interacting medium phenomenologically in terms of quasiparticle excitations with medium-dependent self-energies. We show that the resulting transport coefficients reproduce the parametric dependencies on temperature and coupling obtained in perturbative QCD at large temperatures and small running coupling. The extrapolation into the nonperturbative regime results in a decreasing specific shear viscosity with decreasing temperature, exhibiting a minimum in the vicinity of the deconfinement transition, while the specific bulk viscosity is sizable in this region, falling off rapidly with increasing temperature. The temperature dependence of specific shear and bulk viscosities found within this quasiparticle description of the pure gluon plasma is in agreement with available lattice QCD results.

During the last years, the new laser based technology of particle acceleration was developed at such a rate that medical application, i.e. for cancer therapy, becomes entirely conceivable. Promising more compact and economic proton accelerators, being suitable for existing radiotherapy hospitals, the laser technology however results in ultra-short pulsed particle beams of ultra-high pulse dose and pulse dose rate. Thus, the consequences of laser particle acceleration on beam transport and radiation field formation, dosimetry and radiobiological effects have to be investigated carefully for the whole translational chain from bench to bedside.
Within the German joint research project “onCOOPtics” systematic in vitro cell experiments aiming on the influence of the ultra-high pulse dose rate were firstly established at the Jena 10 terawatt laser system JETI that provides laser accelerated electrons of some ten MeV. Secondly, the increased laser intensity of the 150 terawatt laser system DRACO at the HZDR was applied to accelerate protons to energies of up to 20 MeV. Previous to these experiments, both laser systems had to be extensively optimized in terms of intensity, energy distribution, background reduction, spot size, stability and reliability of the particle beams. The combination of real-time monitoring of dose delivery and a precise retrospective absolute dosimetry enabled the application of defined doses, in spite of the laser based fluctuations of beam intensity and energy. For comparison, reference irradiations with conventionally accelerated, continuous particle beams were performed in parallel to each laser experiment.
In consequence, all key requirements necessary for systematic in vitro cell experiments as the basic translational step towards clinical application of laser-driven particle beams have been fulfilled. Moreover, the dose response curves obtained for pulsed and continuous particle beams show no significant influence of the ultra-high pulse dose rate on the radiobiological response. As next step, animal studies that demand for the translation from 2D to 3D irradiation are in preparation.
The work was supported by the German Federal Ministry of Education and Research (BMBF), grant no. 03ZIK445.

Ion implantation can be a very useful technique to dope silicon nanowires heavily to improve their electrical properties. However, heavy implantation can amorphize the nanowires completely. Subsequently, a complete recovery of their crystallinity, which is of utmost importance to ensure their improved electrical properties, becomes nontrivial. We have performed a controlled study of nanowire recrystallization using vertical Si < 111 > nanowires that were amorphized during doping by arsenic ion implantation. Upon a single-step thermal anneal by furnace (500-650 degrees C) or by rapid thermal annealing (800-1200 degrees C), the nanowires turned partly single-crystalline from the bottom and partly polycrystalline from the top, owing to a competition between solid phase epitaxial regrowth from the substrate and random nucleation and growth, probably originating from the free surface. A complete recrystallization of the amorphized nanowires was achieved only after the furnace-annealed nanowires were annealed for a second time at a higher temperature (950-1200 degrees C). The polycrystalline grains formed during the first anneal were successfully aligned to the < 111 > direction, leading to a recovery of the single-crystalline structure of the nanowires.

Complex effect of different contributions (spontaneously formed In nanoparticles, near-interface, surface, and bulk layers) on electrophysical properties of InN epitaxial films is studied. Transport parameters of the surface layer are determined from the Shubnikov-de Haas oscillations measured in undoped and Mg-doped InN films at magnetic fields up to 63 T. It is shown that the In nanoparticles, near-interface, and bulk layers play the dominant role in the electrical conductivity of InN, while influence of the surface layer is pronounced only in the compensated low-mobility InN:Mg films.

The generation and characterization of narrowband THz pulses by means of chirped pulse difference frequency generation in Auston-switch type photoconductive antennas is reported. Using optical pulses with energies in the range from 1 nJ to 1µJ, we generate THz pulses with up to 50 pJ in energy and electric field strengths on the order of 1 kV/cm. Two emitter concepts are investigated and circumvention of the fast saturation for small area excitation by scaling of the THz emitter is demonstrated.

Aims: Leukotriene levels increase in cerebrospinal fluid following controlled cortical impact (CCI) injury in rats. We investigated the impact of leukotrienes on contusion size by the effect of two different leukotriene inhibitors in the CCI model.

Methods: 92 male Sprague-Dawley rats were investigated at 24h and 72h after CCI with MRI (n= 40) and immunohistochemistry (n=52). Animals received vehicle or either MK886, an inhibitor of 5-lipoxygenase activating protein, or Boscari, a mixture of boswellic acids, acting as competitive non-redox 5-lipoxygenase inhibitors prior to trauma and then every 8 hours until sacrifice.

Results: Global ICP was within normal limits and unaffected by treatment. T2 weighted MRI showed a reduction of lesion volume in treatment groups at 72h by -21% (p<0.01), which was reflected in a smaller lesion area determined from a NeuN labelled section (-17% to -20%, p<0.05). Qualitative characterization by triple immunofluorescence and Fluorojade B staining showed progressive rarefaction of neurons, glia and vasculature in the contusion core, whereas in the pericontusional zone astro- and microglia were up-regulated in the presence of dying neurons. Treatment resulted in an improved survival of NeuN labelled neurons in the pericontusional cortex (+15% to +20%, p<0.05).

Conclusions: Two differently acting leukotriene inhibitors lead to an attenuation of lesion growth and improved pericontusional neuronal survival following CCI. Therefore, leukotrienes seem to be involved in brain contusion growth and pericontusional secondary injury. Leukotriene inhibition should be further investigated as therapeutic option to counteract secondary growth of traumatic brain contusions and to possibly improve pericontusional neuronal survival.

Szabó and Grenthe (Inorg. Chem. 2007, 46, 9372-9378) suggested from NMR spectroscopy that the “yl”-oxygen exchange in dioxo uranium(VI) ion in acidic solution occurs via an OH-bridged binuclear complex (UO₂)₂(μ-OH)₂ ²⁺. Here, an “yl”-oxygen exchange pathway involving the (UO₂)₂(μ-OH)₂ ²⁺ is studied by B3LYP density functional theory calculations. The oxygen exchange takes place via an intramolecular proton shuttle between the oxygen atoms in (UO₂)₂(μ-OH)₂(H₂O)₆ ²⁺. The direct proton transfer from the hydroxo bridge or from the coordinating water to the “yl”-oxygen in (UO₂)₂(μ-OH)₂(H₂O)₆ ²⁺ appears to be negligible because of an exceedingly high activation barrier (~ 170 kJ mol^-1). The exchange mechanism in (UO₂)₂(μ-OH)₂(H₂O)₆ ²⁺ can be described by a multi-step pathway that leads to the formation of an oxo bridge between two uranyl(VI) centers (U-O_yl-U bridge). The activation enthalpy Δ^‡ H of the reaction obtained at the B3LYP level is 94.7 kJ mol^-1 and is somewhat larger than the experimental value of 80 ± 14 kJ mol^-1. However, the discrepancy between theory and experiment is at the acceptable level. The formation of an oxo bridge between the two uranyl(VI) centers was found to be the key step in proton shuttling, indicating that uranyl(VI) complexes with a stable oxo bridge (such as trinuclear (UO₂)₃(μ₃-O)(OH)₃ ⁺) may have even faster “yl”-oxygen exchange rates than (UO₂)₂(μ-OH)₂ ²⁺.

The radionuclide ⁶⁰Fe is an important nuclide in nuclear astrophysics. Its half-life has been determined with a sample from a copper beam dump at PSI. After characterization of the beam dump and an intense chemical preparation the final sample material was measured to determine the half-life. This was done with an activity measurement in Munich and a number of ⁶⁰Fe atoms measurement at PSI. This results in a half-life of (2.62 +/- 0.04) Myr [1].
Some of the important aspects of the work will be reported.
References
[1] G. Rugel, T. Faestermann, K. Knie, G. Korschinek, M. Poutivtsev, D. Schumann, N. Kivel, I. Günther-Leopold, R. Weinreich, M. Wohlmuther, Phys. Rev.Lett. 103, 072502.

Batch sorption experiments and time-resolved luminescence spectroscopy investigations were carried out to study the U(VI) speciation in calcium silicate hydrates for varying chemical conditions representing both fresh and altered cementitious environments. U(VI) uptake was found to be fast and sorption distribution ratios (R-d values) were very high indicating strong uptake by the C-S-H phases. In addition a strong dependence of pH and solid composition (Ca:Si mol ratio) was observed. U(VI) luminescence spectroscopy investigations showed that the U(VI) solid speciation continuously changed over a period up to 6 months in contrast to the fast sorption kinetics observed in the batch sorption studies. Decay profile analysis combined with factor analysis of series of spectra of U(VI) - C-S-H suspensions, recorded with increasing delay times, revealed the presence of four luminescent U(VI) species in C S H suspensions, in agreement with the batch sorption data. Along with the aqueous UO2(OH)(4)(2-) species and a Cauranate precipitate, two different sorbed species were identified which are either bound to silanol groups on the surface or incorporated in the interlayer of the C-S-H structure.

A microscopic magnetic model for alpha-Cu₂P₂O₇ is evaluated in a combined theoretical and experimental study. Despite a dominant intradimer coupling J₁, sizable interdimer couplings enforce long-range magnetic ordering at T_N = 27 K. The spin model for a-Cu₂P₂O₇ is compared to the models of the isostructural beta-Cu₂V₂O₇ and alpha-Cu₂As₂O₇ systems. As a surprise, coupled dimers in a-Cu₂P₂O₇ and alternating chains in alpha-Cu₂As₂O₇ contrast with a honeycomb lattice in beta-Cu₂V₂O₇. We find that the qualitative difference in the coupling regime of these isostructural compounds is governed by the nature of AO₄ side groups: d elements (A = V) hybridize with nearby O atoms forming a Cu-O-A-O-Cu superexchange path, while for p elements (A = P, As) the superexchange is realized via O-O edges of the tetrahedron. Implications for a broad range of systems are discussed.

Electron paramagnetic resonance (EPR) spectra of Cu(en)(H₂O)₂SO₄ (en = ethylendiamine) single crystals were measured in the X-band range at temperatures 4 K and 300 K in magnetic fields up to 0.5 T. The angular dependence of the g-factor and EPR linewidths were studied. The analysis of the g-factor confirmed, that coordinating ligands around the Cu(II) ion form a distorted octahedron elongated along the local z axis and the distortion is maintained down to low temperatures. The increase of the linewidth observed at low temperatures can be ascribed to the onset of short-range magnetic correlations previously observed in specic heat studies. The reduction of the period in the angular dependence of the linewidth observed at 4 K cannot be explained by the existence of two crystallographic non-equivalent Cu(II) positions. The analysis of the angular dependence of the linewidth suggests the potential occurence of Dzyaloshinski-Moriya interaction and anisotropic exchange coupling in CUEN.

Due to recent progress in theory and the growing number of physical realizations, low-dimensional quantum magnets continue to receive a considerable amount of attention. They serve as model systems for investigating numerous fascinating phenomena in materials with cooperative ground states, in particular, induced by high magnetic fields. The way a magnetic field changes the ground-state properties and, correspondingly, the low-energy excitation spectrum of low-dimensional magnets is one of the fundamental aspects in quantum magnetism. Here, magnetic excitations in copper pyrimidine dinitrate, a spin-1/2 antiferromagnetic chain with alternating g-tensor and Dzyaloshinskii-Moriya interactions that exhibits a field-induced spin gap, are probed by means of pulsed-field electron spin resonance spectroscopy in fields up to 63 T. In particular, we report on a minimum of the gap in the vicinity of the saturation field Hsat = 48.5 T associated with a transition from the sine-Gordon region (with soliton-breather elementary excitations) to a spin-polarized state (with magnon excitations). This interpretation is fully confirmed by the quantitative agreement over the entire field range of the experimental data with the DMRG investigation of the spin-1/2 Heisenberg chain with a staggered transverse field

The antiferromagnet GdAg₂ has been shown to be a good model system for the magnetoelastic paradox (MEP), because it exhibits large symmetry conserving magnetoelastic strains and the antiferromagnetic propagation vector breaks the tetragonal lattice symmetry (therefore a large symmetry breaking magnetoelastic strain can be expected in a single q magnetic structure). As in many similar Gd based compounds no symmetry breaking strain has been found in the experiment. In order to investigate this MEP further, we have measured magnetostriction and magnetization on a textured polycrystal. The behaviour closely resembles that of GdNi₂B₂C, the prototype system for the magnetoelastic paradox (MEP). Our forced magnetostriction data indicate that the crystal distorts in applied magnetic field and gives further evidence that the MEP is a low field effect. The observed phase transitions are in agreement with available specific heat and neutron diffraction data. Moreover, the saturation magnetic field was measured in high pulsed magnetic fields and agrees well with the value calculated from the Standard Model of Rare Earth Magnetism (SMREM).

Cluster dynamics (CD) is used to study the evolution of the size distributions of vacancy clusters (VC), self-interstitial atom (SIA) clusters (SIAC) and Cr precipitates in neutron irradiated Fe-9at%Cr and Fe-12.5at%Cr alloys at T = 573 K with irradiation doses up to 1.5 dpa and a flux of 140 ndpa/s. Transmission electron microscopy (TEM) and small angle neutron scattering (SANS) data on the defect structure of this material irradiated at doses of 0.6 and 1.5 dpa are used to calibrate the model. For both alloys a saturation behavior was found by CD for the free vacancy and free SIA concentrations as well as for the number density of the SIAC for the doses above 0.006 dpa. The CD simulations also indicate the presence of VC with radii less than 0.5 nm and a strong SIAC peak with a mean diameter of about 0.5 nm, both invisible in SANS and TEM experiments. CD modeling of Cr precipitates has been done with taking into account of deviation of this system from the ideal cluster gas. A specific surface tension of about 0.17 J/m2 between the alpha matrix and the Cr-rich alpha' precipitate and the rate at which Cr monomers are absorbed about 7.94 m-1 were found as best fit values for reproducing the long-term Cr evolution in the irradiated Fe-12.5%Cr alloys observed by SANS. Taking into account the formation and migration of Fe-Cr interstitial as additional link between the CD master equations for the self-defects and the CD master equations for the Cr precipitates, may lead to improve CD results for irradiated Fe-9at%Cr alloy. The assumption on the constant composition of Fe-Cr precipitates under neutron irradiation has been checked by means of new master equation of CD respect of the distribution function of clusters not only on size but also on composition. The slight dependence of the composition on the size of Fe-Cr precipitates is found.

The two-dimensional organic conductor κ-(BEDT-TTF)₂Cu[N(CN)₂]Br_xCl_1−x undergoes a transition from an insulator to a superconductor upon substituting Cl by Br. We have performed in and out-of-plane electric-transport measurements on the alloyed series with x = 20%, 40%, 70%, 80%, 85%, and 90% as a function of temperature in order to explore the bandwidth-controlled phase transition between the Mott insulator and the Fermi-liquid. All crystals exhibit a similar semiconducting behavior of ρ(T) from room temperature down to 100 K. Below approximately 50 K, a metal-to-insulator transition is found for compounds with x < 70%. Out of this Mott insulating state, magnetic order develops below T_N ≈ 25 K. The Br-rich samples cross a bad-metal regime before they become coherent metals and eventually superconducting at T_c ≈ 12 K. For these systems the resistivity at T_c ≤ T ≤ T₀ reveals a ρ(T) ∝ T² dependence associated with a strongly correlated Fermi-liquid, limited by some characteristic temperature T₀. The conclusions are corroborated by data from microwave, magnetic and optical experiments.

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr₂O₄ show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the [111] direction with a theory based on an exchange-striction mechanism leads to an estimate of the strength of the magnetoelastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction is discussed.

A high-field study of magnetization (up to 68 T) and magnetoelastic properties (up to 60 T) of Er₂Co₁₇ is reported. The most significant effect, a first-order transition from the collinear ferrimagnetic to a canted state, is observed at about 40 T with H || [001]. The transition is accompanied by a prominent magnetization jump as well as by step-wise anomalies of the magnetoelastic properties. Thus, the volume of the crystal reduces by about 4 per mil, while the speed of transverse sound in the [001] direction increases by as much as 5 per mil. At higher temperatures the anomalies gradually become smaller and less sharp before they finally disappear at ∼50 K. The anisotropy constants of the Er sublattice and the molecular field thereon have been determined from the magnetization curves.

Nuclear Magnetic Resonance (NMR) experiments in pulsed high magnetic fields up to 62 Tat the Dresden High Magnetic Field Laboratory (Hochfeld-Magnetlabor Dresden) are reported. The time dependence of the magnetic field is investigated by observing various free induction decays (FIDs) in the vicinity of the maximum of the field pulse. By analyzing each FID's phase and its evolution with time the magnetic field's time dependence can be determined with high precision. Assuming a quadratic or cubic dependence on time near the field maximum its confidence is found to be better than +/- 0.03 ppm at low fields and +/- 0.8 ppm near 62 T. In turn, the thus obtained time dependence of the field can be used to demodulate and phase-correct all FIDs so that they appear phase-locked to each other. As a consequence signal averaging is possible. The increase in signal-to-noise ratio is found to be close to that expected theoretically. This shows that the intrinsic time dependence of the pulsed fields can be removed so that the NMR signals appear to be taken at rather stable static field. This opens up the possibility of performing precise shift measurements and signal averaging also of unknown, weak signals if a reference signal is measured during the same field pulse with a double-resonance probe.

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Due to recent progress in theory and the growing number of physical realizations, low-dimensional quantum magnets continue to receive a considerable amount of attention. They serve as model systems for investigating numerous fascinating phenomena in materials with cooperative ground states, in particular, induced by high magnetic fields. In this presentation I will focus on high-frequency and high-field Electron Spin Resonance (ESR) studies of copper pyrimidine dinitrate (Cu-PM), a spin-1/2 Heisenberg antiferromagnetic chain system with alternating g-tensor and Dzyaloshinskii-Moriya interactions in magnetic fields up to 63 T. Due to the alternations, this material exhibits a field-induced gap, observed by us directly. Signatures of three breather branches and a soliton are identified in magnetic fields up to 25 T. The experimental data are sufficiently detailed to make a very accurate comparison with predictions based on the quantum field sine-Gordon theory. We report also on a minimum of the gap in the vicinity of the saturation field Hsat = 48.5 T associated with a transition from the sine-Gordon region (with soliton-breather elementary excitations) to a spin-polarized state (with magnon excitations). This interpretation is fully confirmed by the quantitative agreement over the entire field range of the experimental data with the DMRG investigation of the spin-1/2 Heisenberg chain with a staggered transverse field.

Superconductivity and magnetic order, two fundamental ground states of condensed matter, are observed to be competitive in many materials. In the case of predominantly ferromagnetic exchange interactions, superconductivity is suppressed in almost any representative. The quantity of materials, however, in which a coexistence of superconductivity and ferromagnetism might be studied, could be larger than ever thought.
Here we demonstrate the coexistence of superconductivity and ferromagnetism in Bi3Ni nanostructures which have been prepared by making use of novel chemical-reaction paths. We have characterized their magnetic and superconducting properties by means of magnetometry and electrical-transport measurements. Other than in bulk geometry, submicron-sized particles and quasi one-dimensional nanoscaled strains of single-phase Bi3Ni undergo ferromagnetic order [1]. Superconductivity in confined Bi3Ni emerges in the ferromagnetically ordered phase and is stable up to remarkably high magnetic fields. Uniquely, ferromagnetic hysteresis at zero resistance is observed in nanostructured Bi3Ni. As a result, a magnetic hysteresis loop occurs while the material is in the superconducting state.
The coexistence of superconductivity with ferromagnetic order would most likely be possible in the case of triplet pairing. The absence of an inversion center of the lattice of confined Bi3Ni would allow for the formation of an antisymmetric spatial component of the electron-wave function and could lead to a significant admixture of a spin-triplet component of the order parameter. However, as the lattice of bulk Bi3Ni is centrosymmetric, the question remains as to whether the loss of structural long-range order at the surface of confined nanostructures could induce antisymmetry of the charge carrier wave function. Nuclear magnetic resonance experiments in high magnetic fields* may now open a chance to get deeper insight in the symmetry of the superconducting wave function in k space.