Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

RES³T – the Rossendorf Expert System for Surface and Sorption Thermodynamics – is a digitized thermodynamic sorption database utilizing surface complexation models (SCM). It is mineral-specific and can therefore also be used for complex models of solid phases such as rocks or soils. As to the knowledge of the authors there is no such digital thermodynamic database for surface complexation equilibria existent worldwide, despite of the vast amount of available data.
Data records comprise of mineral properties, specific surface area values,characteristics of surface binding sites and their protolysis, sorption ligand information, and surface complexation reactions. An extensive bibliography is also included, providing links not only to the above listed data items, but also to background information concerning surface complexation model theories, surface species evidence, and sorption experiment techniques.
An integrated user interface helps users to access selected mineral and sorption data, to extract internally consistent data sets for sorption modeling, and to export them into formats suitable for other modeling software. It assists the identification of critical data gaps, the evaluation of existing parameter sets, consistency tests and the establishing of selected reference data sets.
RES³T is implemented as a relational database under MS ACCESS. The database is intended for an international use and is currently converted into a WWW-based version.
A system for illustrating the current blind predictive capabilities of SCM using the RES³T database is the Cu²⁺ sorption onto iron oxyhydroxides. To keep the number of parameters at a minimum, the Diffuse Double Layer model was selected to account for electrostatics. The calculation was performed with the FITEQL code, version 3.2. The respective SCM parameters from RES³T were the binding site density for the minerals, the surface protolysis constants, and the brutto stability constants for all relevant surface complexes. The model prediction almost always represented the experimental values for the sorbed amount of Cu²⁺, expressed as conventional distribution coefficients K_D as required by PA software.

Mit Batch- und Durchflussexperimenten wurde, unter Einbeziehung der Mineralauflösung und Sekundärphasenbildung, die U(VI) Sorption auf zwei unterschiedlichen Chloritmineralen untersucht. Hierbei handelte es sich um einen nicht alterierten Ripidolith Chlorit (CCa-2) von Flagstaff Hill (El Dorado County, California, USA), der aus einem Chloritschiefer gewonnen wurde und einen hydrothermal alterierten Chlorit von Grimsel (Schweiz), der aus einer granitischen Kluft gewonnen wurde. Die Durchflussexperimente wurden mit 0,5 g des jeweiligen Chloritpulvers (63-200 µm Korngröße), einer 0.1 M NaClO4-Ausgangslösung, einer U(VI)-Konzentration von 1´10-6 M und bei einem pH von 6,5 durchgeführt. Die Ergebnisse zeigten einen deutlichen Unterschied im Sorptionsverhalten der beiden Chlorite. Der nicht alterierte CCa-2 Chlorit zeigte ein Sorptionsmaximum von 90 % und wies damit eine mehr als 20 % höhere Sorption unter vergleichbaren Bedingungen als der hydrothermal alterierte Chlorit auf. Vorangegangene Untersuchungen am CCa-2 Chlorit [1] und Grimsel Chlorit [2] zeigten, dass diese erhöhte Sorption auf die Bildung von Fe-oxyhydroxiden, wie beispielsweise Ferrihydrit, während der Auflösung des nicht alterierten Chlorits zurückgeführt werden können. Ferrihydrit ist aufgrund seiner hohen spezifischen Oberfläche und seiner hohen Sorptionsaffinität ein wichtiger Sorbent für U(VI). Der alterierte Grimsel Chlorit wurde bereits im hydrothermalen Stadium gelaugt, so dass dieser nicht so stark zur Sekundärphasenbildung neigt wie der CCa-2 Chlorit. Die unterschiedlichen U(VI) Sorptionsergebnisse an den beiden Chloriten belegen diese Interpretation.
/1/ Krawczyk-Bärsch et al. (2003): Chem. Geol. (submitted).
/2/ Arnold et al., (1998): Chem. Geol. 151, 129-141.

Bei stark exothermen Batch- und Semibatch-Prozessen ist die Identifikation des aktuellen Prozesszustandes und die frühzeitige Erkennung von unerwünschten Betriebszuständen sowohl unter dem Aspekt der Anlagen- und Umweltsicherheit als auch aus Gründen der Sicherung einer gleichbleibend hohen Ausbeute und Produktqualität von besonderer Bedeutung. Zur Unterstützung des Bedienungspersonals hinsichtlich einer optimalen Anlagenfahrweise wurde ein auf adaptiven Energie- und Stoffbilanzen basierendes Online-Monitoring-System (MoSys) konzipiert. Die Systementwicklung erfolgte anwendungsorientiert für heterogen katalysierte Hydrierprozesse von Nitroaromaten in Rührkesselreaktoren. Für den Einsatz des Systems im Industriemaßstab wurde MoSys in ein komplexes Batch-Informations-Management-System (BIMS) eingebunden. Somit ist die Anzeige der MoSys-Ergebnisse, wie Umsatz- und Konzentrationsverläufe, simultan zu den primären Prozesssignalen und den chargenorientierten Informationen an den verschiedenen Operatorstationen in der Chemieanlage möglich. Der Test des Zustandserkennungssystems erfolgte an einer Mehrzweckanlage der DEGUSSA AG im Werk Radebeul.
Gezeigt werden der prinzipielle Aufbau des Monitoring-Systems (Berechnungsalgorithmus), die Einbindung und Funktion von MoSys innerhalb des Batch-Informations-Management-Systems sowie die Visualisierung der MoSys-Ergebnisse an den Operatorstationen am Beispiel von einzelnen Screenshots. Die Validierung des Systems an der Industrieanlage ist am Beispiel von Konzentrations- und Umsatzverläufen sowie der Zustandsklassifikation für die Zwischenproduktakkumulation dargestellt. Eine Zusammenfassung, in der die Bedeutung des Einsatzes von BIMS/MoSys für die industrielle Praxis aufgezeigt wird, beschließt den Artikel.

Mittels zeitaufgelöster laserinduzierter Fluoreszenzspektroskopie (TRLFS) wurde die Uranyl(VI) Sorption auf dem Schichtsilikatmineral Muskovit angewendet. Ziel dabei war es, die adsorbierten Oberflächenspezies sowohl auf den Basisflächen als auch auf den Kantenflächen nachzuweisen und zu vergleichen.
Die Muskovit Plättchen wurden dazu bei pH 6.3 für ca. 60 h mit einer 1×10-5 M Uranyl Lösung (0,1 N NaClO4) kontaktiert. Etwa 72 % der Ausgangsmenge an Uranyl wurde unter diesen Bedingungen sorbiert.
Auf den Basisflächen wurde kein Uranyl-Fluoreszenzspektrum erhalten, was zeigt, dass Uranyl vernachlässigbar sorbiert wurde (< 10-12 M/cm2). Die Sorption erfolgt dominierend an den Kantenflächen. Die Spektrenauswertung ergab das Vorliegen von zwei sorbierten Uranylspezies mit Lebensdauern von 1,15 bzw. 9,65 µs. Die Lage der Hauptemissionsbanden stimmen innerhalb der Fehlergrenzen für beide Komplexe überein, was auf eine unterschiedliche Anzahl der umgebenden Wassermoleküle hinweist. Aus diesen Ergebnissen und zusätzlich durchgeführten EXAFS Untersuchungen lässt sich die Sorption von Uranyl(VI) an den Muskovit Kantenflächen am besten mit zwei bidentaten mononuklearen Oberflächenspezies beschreiben.

During the last decades, the focused ion beam (FIB) became a very useful and versatile tool in the microelectronics industry, as well as in the field of research and development. For special purposes like writing ion implantation or ion mixing in the µm- or sub-µm range different ion species are needed. Therefore alloy liquid metal ion sources (LMIS) are used. The energy distribution of the ions from an alloy LMIS is one of the determining factors for the performance of an FIB column. Different source materials like Au73Ge27, Au82Si18, Au77Ge14Si9, Co36Nd64, Er69Ni31, and Er70Fe22Ni5Cr3 were investigated with respect to the energy spread of the different ion species as a function of emission current I, ion mass m and emitter temperature T. For singly charged ions the predicted dependence of the energy spread, DE µ I2/3 m1/3 T1/2 found for Ga could be confirmed. The alloy LMIS`s discussed above have been used in the Rossendorf FIB system IMSA-100 especially for writing implantation to fabricate sub-µm pattern without any lithographic steps. A Co-FIB was applied for the ion beam synthesis of CoSi2 micro-structures. Additionally, the possibility of varying the current density with the FIB by changing the pixel dwell-time was used for radiation damage investigations in Si and SiC at elevated implantation temperatures. Furthermore, a broad spectrum of ions was employed to study the sputtering process depending on temperature, angle of incidence and ion mass on a couple of target materials using the volume loss method. Especially this technique was used for the fabrication of various kinds of micro-tools.
All these examples underline the importance of FIBs in modern research and the new possibilities opened up by a mass separated system applying a broad spectrum of ion species.

The aim of the investigation is the growth of high-precision single crystals of intermetallic compounds using well defined magnetic fields. The fundamental problem is conditional on the fact that especially complicated intermetallic compounds are not producible as single crystals over the whole cross-section by the inductive floating-zone melting technique since the geometry of the zone at the solid-liquid-interface is unfavourable. The controlled adjustment of a solid-liquid-interface of desired curvature and the knowledge of the melt convection in liquids with high conductivity can be arranged by the contact-less influence of electromagnetic fields. Numerical simulations for the determination of the electromagnetic field configuration induced by the RF heater coil and the solution of the coupled heat and hydrodynamic equations were done for the model substance Ni [1]. The significant influence of the electromagnetically driven flow, which acts opposite to the Marangoni convection, makes the solid-liquid interface concave towards the melt.
Comprehensive investigations of the influence of growth parameters such as zone length, power influence and heated region on the solid-liquid interface geometry during RF floating zone crystal growth were carried out experimentally. It could be shown that undesired concave (towards the melt) interface regions cannot be avoided even at optimised parameter configurations [2].
As a result, a two-phase magnetic field pump, which allows a strong manipulation of the convection and therefore of the solid-liquid interface, was designed. It allows to change the flow structure from the typical double vortex to a single one with a strong influence on the phase boundary shape (Fig. 1). The adjustment of a complete convex solid-liquid interface shape in RF-floating zone crystal growth was tackled with this additional melt stirring resulting in a definite improvement of the solid-liquid-interface.

For the purification of uranium contaminated waters various water purification methods (e.g., application of ion exchangers, direct precipitation, microbiological methods) are usually applied. Also solvent extraction applying calix[6]arenes is suitable to separate uranium from aqueous solution [1]. To facilitate the uranium separation from uranium containing waters in practice, we are developing an alternative procedure. For this, calix[6]arenes are permanently fixed onto textile substrates via spacer groups [2]. This method is advantageous especially for smaller remediation objects and objects with lower contamination levels ([UO22+] ~ 1×10-6 M).
In the present work, the extraction efficiency of various calix[6]arenes including their selectivity towards uranium(VI) is studied in a two phases solvent extraction system in dependence on pH value, ligand concentration and the amount of competing ions. The complex formation between uranium(VI) and calix[6]arenes is further studied at pH 4 by means of TRLFS as well as by TRLFS with ultrashort laser pulses. By these methods it is possible to detect uranium and calixarene species at equilibrium directly in the aqueous and organic phase. Reaction mechanisms are discussed and extraction constants are determined. In the presence of competing ions (e.g., calcium, barium, magnesium) the uranium extraction is only slightly decreased. The suitability of the calix[6]arenes as efficient reagents for selective uranium separation from aqueous solution is shown.

[1] Shinkai, S. et al.: Molecular design of calixarene-based uranophiles which exhibit remarkably high stability and selectivity. J. Am. Chem. Soc. 109, 6371-6376 (1987).
[2] Schmeide, K. et al.: Separation of uranium from aqueous solution by textile bound calixarenes. In: Uranium in the aquatic environment. Springer Verlag, Berlin 2002, p. 417-424.

Heavy ion therapy has two definite advantages: good dose localization and higher biological effect. Range calculation of the heavy ions is an important factor in treatment planning. X-ray CT numbers are used to estimate the heavy ion range by looking up values in a conversion table which relates empirically photon attenuation in tissues to particle stopping power; this is one source of uncertainty in the treatment planning. Use of positron emitting radioactive beams along with a positron emission tomograph or a positron camera gives range information and may be used as a means of checking in heavy ion treatment planning. However, the metabolism of the implanted positron emitters in a living object is unpredictable because the chemical forms of these emitters are unknown and the metabolism is dependent on the organ species and may be influenced by many factors such as blood flow rate and fluid components present. In this paper, the washout rate of ¹¹C activity implanted by injecting energetic ¹¹C beams into thigh muscle of a rear leg of a rabbit is presented. The washout was found to consist of two components, the shorter one was about 4.2+-1.1 min and the longer one ranged from 91 to 124 min. About one third of the implanted positron activity can be used for imaging and the rest was washed out of the target area.

A relative biological effectiveness (RBE) not much larger than unity is usually assumed for soft x-rays (up to ~50 keV) that are applied in diagnostic radiology such as mammography, in conventional radiotherapy and in novel radiotherapy approaches such as x-ray phototherapy. On the other hand, there have been recent claims of an RBE of more than 3 for mammography and respective conventional x-rays. Detailed data on the RBE of soft x-rays, however, are scarce. The aim of the present study was to determine the effect of low-energy x-rays on chromosomal damage in vitro, interms of micronucleus induction. Experiments were performed with 25 kV x-rays and a 200 kV x-ray reference source. The studies were carried out on primary human epidermal keratinocytes (HEKn), human fibroblasts (HFIB) and NIH/3T3 mouse fibroblasts. Micronucleus (MN) induction was assayed after in vitro irradiation with doses ranging from 1 to 5.2 Gy. Compared to the effect of 200 kV x-rays, 25 kV x-rays resulted in moderately increased chromosomal damage in all cell lines studied. This increase was observed for the percentage of binucleated (BN) cells with micronuclei as well as for the number of micronuclei per BN cell.
Moreover, the increased number of micronuclei per micronucleated BN cell in human keratinocytes and 3T3 mouse fibroblasts suggests that soft x-rays induce a different quality of damage. For all cell lines studied the analysis of micronucleus induction by 25 kV soft x-rays compared to 200 kV x-rays resulted in an RBE value of about 1.3. This indicates a somewhat enhanced potential of soft x-rays for induction of genetic effects.

To study of the complex formation of dihydroxybenzoic acids with uranium(VI), we measured the spectra of 2,5-dihydroxybenzoic acid (2,5-DHBA) as a function of pH (2.0 - 4.0) and concentration of uranium (0 - 5x10-3 M). The intensity of the spectra changes with pH and uranium concentration. As we found only spectra with one emission maximum and mono-exponential fluorescence decay, we concluded that no excited state reactions could be observed in the experimental conditions. On the other hand, a change in the fluorescence lifetime could be obtained. The fluorescence lifetimes were found to be in the range from 1.8 ns to 5.7 ns. This means that a dynamic quench process occurred. In order to estimate the formation constant of the 2,5-DHBA with uranium, firstly, we evaluated the protonation constant of the carboxylic group of the 2,5-DHBA. It was found to be log K3 = 2.77 ± 0.05, by taking into account the self-quenching effect. This is in good agreement with literature data (2.82) /1/. The 2,5-DHBA itself and uranium quench the fluorescence of the 2,5-DHBA. We evaluated the dynamic quench constants to be KSV = 216 ± 4 for the ligand itself and KSV = 45 ± 1 for uranium. Both have to be taken into consideration for estimating the complex formation constant. Furthermore, in the pH range 2.0 to 4.0, slopes between 0.91 and 1.39 were found for the validation of the stoichiometry. We conclude, therefore, that a one to one complex forms between uranium and 2,5-DHBA. The dependence of the formation constants on pH values was investigated in order to determine the number of protons involved in the complex formation. Since the slope of the pH dependence was -0.79 ± 0.1, we conclude that one proton at most is involved in this complex formation. This suggests that only the carboxylic group is involved in the complex formation. Based on these considerations, the complex formation constant was assigned to be log K = -0.57 ± 0.26. As uranium shows fluorescence properties, the complex formation can be also confirmed using the changes in the fluorescence behavior of uranium. The formed complex itself does not show fluorescence properties, and only the emission of the non-complexed uranium is observed. As example at pH 4.0, formation constants of log K = 3.29 ± 0.16 were assigned for the ligand study and of log K = 3.17 ± 0.32 for the uranium study, respectively./1/ L. Lajunen, R. Portanova, J. Piispanen et al; Pure & Appl.Chem.,69,329 (1997)

In a former study we analyzed the complex formation between uranium and 2,3-dihydroxybenzoic acid using the fluorescence properties of the ligand. The formation constant was found to be log K11 = -3.11 ± 0.16.We have validated this complex formation using the fluorescence properties of uranium. The formed complex has no fluorescence properties. This is confirmd by a monoexponetial fluorescence decay and also the fluorescence spectra show no shift in the emission maxima.However the fluorescence lifetime of the non-complexed uranium in the solution depends on the concentration of the added ligand. This is due to the dynamic quench effect of the ligand molecule. This quench effect is strongly correlated to the pH of the solution. This leads to the conclusion that only the protonated ligand effects this quench process. Taking this effect into account we are able to calculate the fluorescence intensities of the non-complexed uranium and by use of these data the complex formation between uranium and 2,3-dihydroxybenzoic acid. We obtained a one to one complex formation accompanied by the release of two protons from the ligand, as also found in the study of the fluorescence properties of the ligand. However the derived complex formation constants differ between both methods. The formation constant obtained from the uranium study was found to be log K = -3.99 ± 0.44. This is about 0.9 orders of magnitude lower compared to the constant derived from the study of the ligand. The confidence limits of the two data sets overlap nevertheless the deviation of the both constants leads to the conclusion that other reactions may be involved. From the uranium fluorescence we do not expect such reactions. But the non-complexed ligand may show separate reactions in the excited state, which lead to a change of the fluorescence intensity of the ligand and resulting in an increase of the calculated formation constant. The consequence of the inclusion of these reactions in the examination leads to an exact determination of the ligand concentration accompanied by a much better agreement of the assigned formation constants.

The paper presents examples illustrating the current blind predictive capabilities of surface complexation models (SCM) and respective databases. High-quality experimemtal sorption data sets as provided by Phase II of the NEA Sorption Project for its fitting assessment efforts were used. The systems covered are Np(V) sorption onto hematite, U(VI) sorption onto quartz and Se sorption onto goethite. To keep the number of parameters at a minimum, the Diffuse Double Layer model was selected to account for electrostatics. All calculations were performed with the FITEQL code, version 3.2. Based on the information in the sorption database RES³T [1] for the above minerals and chemically similar phases, first a set of relevant species was formed. Then respective surface complexation parameters were taken from RES³T: the binding site density for the minerals, the surface protolysis constants, and the brutto stability constants for all relevant surface complexes. To be able to compare and average thermodynamic constants originating from different sources, the normalization concept as introduced by Kulik [2] was applied. Lacking data was substituted by estimates exploiting chemical analogy. The only system-specific parameters directly going into the computations were the solid-liquid ratio and the specific surface area.

The model prediction almost always represented the experimental values for the sorbed amount of Np, U and Se, expressed as conventional distribution coefficients KD as required by PA software, within one order of magnitude or better, provided an adequate chemical system was assumed. Further improvements may arise from a broader data base eliminating the need for data estimations through chemical analogies.

[1] RES³T - Rossendorf Expert System for Surface and Sorption Thermodynamics, V. Brendler, A. Vahle, T. Arnold, G. Bernhard, T. Fanghänel, J.Contaminant Hydrology, in press
[2] Sorption modelling by Gibbs energy minimisation: Towards a uniform thermodynamic database for surface complexes of radionuclides. D. Kulik, Radiochim. Acta, 90 (2002), 815-832

Radiometals play an important role in nuclear medicine^1-3 for the diagnosis or therapy of various diseases. Beside technetium-99m, the most frequently used radionuclide for in-vivo- diagnosis because its optimal nuclide properties, economically supply by the ⁹⁹Mo/^99mTc generator and easy preparation of the ^99mTc-radiopharmaceutical in the clinic, current search for metalloradiopharmaceuticals focuses on both unconventional positron emitting metals (e.g. Cu-64, Ga-66, Y-86, Tc-94m) as potential agents for positron emission tomography (PET) and of radiometal agents labeled with particle emitters for radionuclide therapy³. Since the basic requirement for therapeutic radiopharmaceuticals, namely to induce high effective dose for the target but practically no interference with healthy tissue is not fulfilled yet, the number of therapeutic radiopharmaceuticals for routine use is limited.
Besides the availability of suitable nuclides, the design of chelate systems for stable binding of the radiometal is a crucial point in the development of new metalloradiopharmaceuticals. The chemistry of respective chelates designed in recent years for binding technetium and rhenium at various oxidation states will be discussed. Such chelates involve mixed-ligand complexes containing the metalnitrido core at oxidation state V, Tc(III)/Re(III) and organometallic Tc(I)/Re(I) complexes.
Finally, the application of these chelates for labeling peptides and receptor-affine coordination compounds will be demonstrated.

Visualisation of primary prostate cancer and its metastases remains a clinical important problem, state-of-the-art methods like CT, MRI, TRUS (transrectal ultrasound) and ¹⁸F-FDG PET notwithstanding. The difficulties are even more pronounced in case of local recurrence as ¹⁸F-FDG PET, while useful in the detection of metastases, is not considered helpful in the investigation of relapse. The aim of this study was to evaluate the efficacy of ¹¹C-acetate and ¹⁸F-FDG-PET in the detection of prostate cancer and its metastases in patients treated with or without hormonal ablation.
25 patients (age: 54 to 82 years) were investigated during follow-up of a primary prostate cancer, suspected relapse, or metastatic disease using ¹¹C-acetate PET and 15 with ¹⁸F-FDG PET additionally. 14 Patients had antiandrogen treatment at the time of the investigation, the other 11 patients were drug-naive.
Primary tumours were detected in 20/24 (83%) patients using ¹¹C-acetate PET and in 10/15 (75%) patients using ¹⁸F-FDG PET. Based on the results of both PET scans, one patient was diagnosed with a lung cancer as second malignancy. Median ¹⁸F-FDG uptake exceeded that ¹¹C-acetate in distant metastases (SUV=3.2 vs. 2.3, respectively). ¹¹C-acetate uptake, however, was higher in local recurrence and in local lymph node metastases (median SUVs = 2.9 and 3.8) compared to ¹¹C-acetate (median SUVs = 1.0 and 1.1, respectively). ¹¹C-acetate and ¹⁸F-FDG uptake was lower in patients on antiandrogen therapy compared with the drug-naïve patients but ¹¹C-acetate uptake was not significantly impaired. A close correlation of serum PSA level and Gleason score on the one hand and both ¹¹C-acetate uptake and ¹⁸F-FDG uptake on the other hand was observed.
These data confirm that ¹¹C-acetate is more useful than ¹⁸F-FDG in the detection of local recurrences and localised lymph node metastases. ¹⁸F-FDG, however, appears to be more accurate in visualising distant metastases. Antiandrogen therapy reduces tumour metabolic activity and therefore overall PET accuracy but detection of local recurrences by ¹¹C-acetate is not severly compromised. Ultimately, there may be a role for combined ¹¹C-acetate/¹⁸F-FDG PET in the follow-up of patients with prostate cancer and persisting or increasing PSA.

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The influence of the formation of secondary iron phases on the sorption behavior of U(VI) on chlorite was investigated in batch sorption experiments with two different types of chlorites: an unaltered chlorite from Flagstaff Hill (CCa-2) and a hydrothermally altered chlorite from Grimsel/Switzerland. The easily extractable ions have not been removed in the CCa-2 chlorite and it therefore tends to form secondary phases. In contrast, the hydrothermally altered chlorite is relative resitant to weathering as discussed in Arnold et. al. [1] and therefore does not tend to form secondary phases. The batch sorption experiments were carried out under ambient temperature and pressure using a solid concentration of 0,5 g chlorite in 40 mL 0,1 M NaClO4 solution. The higher sorption capacity of the unaltered CCa-2 chlorite of more than 20 % of the initially added 1´10-6 M U(VI) compared to the hydrothermally altered chlorite is especially striking in the pH region from 6,5 to 8,5 and was attributed to the generation of secondary Fe and Al phases forming during the two months period of the batch sorption experiments. As a consequence of the formation of a new phase additional mineral surface area is generated [2] which serves as a substrate for further uranium sorption. It is well known that Fe-oxyhydroxide particles show a very high affinity for sorbing U(VI) [3]. Our results clearly show that newly-forming secondary phases may increase the sorption capacity of primary minerals. The Diffuse Double Layer Model (DDLM) was applied to model the U(VI) sorption on the two chlorites including the newly-formed secondary phases.

This class of flows is characterized by the feeding of strong electrical currents into a volume of liquid metal. A prominent example of industrial interest is the electrode-welding where the current is supplied via a locally restricted area, leading to high current densities. The interaction of these currents with their own magnetic field drives flows which exhibit phenomena like formation of jets and pinch-effect. Further increasing the current may lead to disruption of the melt column accompanied with a discharge. This can be used for a liquid metal current limiter with self-healing properties.
Local measurements of the flow structures are of obvious interest for a better understanding of these phenomena. The paper will give results from a systematic study of the flow structure performed by means of our mechano-optical velocity probe. The measured flow structure of the evolving jet was found to be in a reasonable agreement with our numerical simulations.

Passing an electrical current through a volume of conducting fluid drives flow via the interaction with its own magnetic field. Among this class of electro-vortical flows the electrode-welding is a prominent example of industrial interest. In such configurations where a strong current is supplied locally, the resulting high current densities show phenomena like formation of jets and pinch-effect. The latter may disrupt the melt column in the case of very strong currents, accompanied by a discharge. Thus pinching can be used for a liquid metal current limiter with self-healing properties.
Local flow measurements are important for a better understanding of these phenomena. This paper gives results from a systematic study of the fluid motion performed with our mechano-optical velocity probe. The measured flow structure of the evolving jet was found to be in a reasonable agreement with our numerical simulations. Local pressure measurements have been consistent with the experimental and numerical results for the flow field.

Nonlinear probing of the fundamental lattice vibration of polar crystals is shown to reveal insight into higher-order cohesive lattice forces. With a free-electron laser tunable in the far infrared we experimentally investigate the dispersion of the second-order susceptibility due to the phonon resonance in GaAs. We observe a strong resonance enhancement of second harmonic light generation at half the optical phonon frequency, and in addition a minimum at a higher frequency below the phonon frequency. Measuring this frequency and comparison to a theoretical model allows the determination of competing higher-order lattice forces.

195-keV Fe+ Ionen wurden mit einer nominellen Dosis von 5x10E16 cmE-2 bei Raumtemperatur in einen GaN(0001)-Wafer implantiert.

Half-sandwich complexes of the type (RCOCp)M(CO)₃] with M ) Re and ^99(m)Tc were synthesized from [M(OH₂)_3-(CO)₃]⁺ in water. The R group can be an organic residue or a receptor binding biomolecule with a spacer to cyclopentadienyl (Cp). This provides a general route to Cp complexes of technetium without the need for starting from [TcBr(CO)₅].
The X-ray structure of [{C_6H5CH₂COC₅H₄}Tc(CO)₃] has been elucidated. The compound crystallizes in the monoclinic space group P2₁/c with a = 16.1454(9), b = 7.6300(6), and c = 12.3922(7) Å and beta = 107.792(6)°. We have chosen a serotonergic receptor ligand (WAY) as an example for the derivatization of Cp with a bioactive molecule. WAY is linked to Cp by an aliphatic chain of variable length. The half-sandwich complexes were prepared from water and organic solvents. The structure of [(WAY4-Cp)Re(CO)₃] could be elucidated. The compound crystallizes in the monoclinic space group P2₁/c with a = 15.7112(6), b = 6.8775(3), and c = 25.5217(12) Å and beta = 103.778(5)°. Quantification of inhibition constants gave a clear structure-activity relationship. A single methylene group between the receptor binding site and the half-sandwich complex gave an IC₅₀ of 217 nM for T_1A, whereas a butylene linker resulted in retention of the inhibition constant with an IC₅₀ of 6 nM with respect to underivatized WAY. For use as radiopharmaceuticals, the compounds have also been prepared with ^99mTc in quantitative yield.

The [¹⁸F]fluoromethyl analogue of (+)-McN5652 ([¹⁸F]FMe-McN) has recently been developed as a radioligand for imaging the neuronal serotonin transporter (SERT) with positron emission tomography (PET). We describe here the autoradiographic evaluation of [¹⁸F]FMe-McN in the brain of rats and pigs. Autoradiographic studies of [¹⁸F]FMe-McN performed on rat and pig brain in vitro showed a high accumulation of radioactivity in the regions rich in SERT, such as amygdala, hypothalamus, superficial gray layer of the superior colliculus, various nuclei of thalamus and substantia nigra. The binding of [¹⁸F]FMe-McN was reduced by citalopram, a highly selective inhibitor for SERT. Similar regional specific binding densities of [¹⁸F]FMe-McN were observed in both species. The regional distribution and specific binding of this radiotracer correlates well with the distribution and regional brain binding of [³H]citalopram. Region-to-cerebellum ratios of [¹⁸F]FMe-McN in vitro reached a maximum value of 20.6 in the rat and 14.5 in the pig. In addition, ex vivo autoradiography of the rat brain was performed 90 min after i.v. administration of [¹⁸F]FMe-McN. The highest regional uptake of [¹⁸F]FMe-McN was observed in the hypothalamic area, substantia nigra and amygdaloid area. There is a high correlation between the in vitro and in vivo binding. The region-to cerebellum ratio in vivo reached a maximum value of 5.1 in the substantia nigra, the highest yet reported for a ¹⁸F-labelled SERT tracer in vivo in this region. Furthermore, the distribution volume of [¹⁸F]FMe-McN calculated from the PET data in various regions of the porcine brain is highly correlated with the SERT density as determined by in vitro autoradiography with [³H]citalopram. Thus, [¹⁸F]FMe-McN has a clear potential as a radiotracer for studies of the SERT distribution in man with PET.

Das vorliegende Projekt hatte die Ermittlung der räumlichen und zeitlichen Verteilung der Kühlmittelparameter am Spaltzoneneintritt bei transienten Prozessen zum Ziel, bei denen an den einzelnen Kühlmitteleintrittsstutzen des Reaktors Unterschiede in der Borkonzentration bzw. in der Kühlmittel-temperatur auftreten. Die Sicherheitsrelevanz ist durch die Auswirkungen von Deborierungs- und Kaltwassertransienten auf die Leistungsfreisetzung im Reaktorkern gegeben.Mit Hilfe von Experimenten an einem Reaktormodell sowie durch Validierung und Nutzung eines dreidimensionalen Fluidynamikcodes (CFX-4) und durch Entwicklung eines vereinfachten Vermischungsmodells (SAPR) wurden die für die Ermittlung der reaktordynamischen Systemantwort notwendigen Tools zur Beschreibung der Verhältnisse am Kerneintritt geschaffen. Mit der Modellierung der räum-lich und zeitlich aufgelösten Bor- bzw. Temperaturverteilung im RDB wurden die Voraussetzungen für die gekoppelte neutronenkinetisch-thermohydraulische Simulation von Deborierungs- und Kaltwas-sertransienten und deren Sicherheitsbewertung entwickelt. Das Vorhaben beschränkt sich auf Vor-gänge ohne Verdampfung des Kühlmittels, die Vermischung innerhalb des Reaktorkerns bleibt aus-geklammert. Um Mehrfachzirkulationen von Temperatur- bzw. Borkonzentrationsstörungen im Pri-märkreis adäquat abbilden zu können, wurde auch die Vermischung im oberen Plenum behandelt. Zur Lösung der Aufgabe wurde die Versuchsanlage ROCOM (Rossendorf Coolant Mixing Model) aufgebaut. ROCOM ist ein 1:5-Modell eines KONVOI DWR. Durch die volle Abbildung aller vier Um-wälzschleifen, die flexible Versuchssteuerung sowie die speziell für ROCOM entwickelte Gittersen-sormesstechnik zur räumlich und zeitlich hochauflösenden Bestimmung von Konzentrationsverteilungen stellt ROCOM heute eine weltweit führende Versuchsanlage dar. Bei den Experimenten wurden transiente Konzentrationsverteilungen am Kerneintritt für alle gemäß Arbeitsplan zu betrach-tenden Szenarien ermittelt und zur Validierung von CFX-4 genutzt. Das vereinfachte Vermischungs-modell SAPR dient zur effizienten Kopplung zwischen dem thermohydraulischen Systemcode und dem dreidimensionalen neutronenkinetischen Kernmodell.

Proper characterization of tin doped indium oxide (ITO) films prepared at various deposition parameters is important to produce the layers with low resistivity and high luminous transmittance. Therefore, thin ITO films were grown on insulating substrates by means of pulsed reactive dual magnetron sputtering at different base pressure, magnetron pulse duration and Ar/O2 ratio. To characterize the layers after deposition, spectroscopic ellipsometry (SE) was applied in combination with optical transmittance and resistivity measurements. Surface roughness obtained by SE was corroborated by atomic force microscopy. A significant variation in film deposition rate was observed for experiments with different magnetron pulse duration due to SE results. It agrees with Auger depth profiling data. The latter also showed that the O/In ratio values close to 1.5 correspond to the lowest film resistivity. For ITO films produced at various deposition conditions it was observed that SE derived free electron parameters ratio demonstrates certain minimum. It corresponds to the lowest film resistivity and high transmittance. SE was also applied in situ as a non contact technique to monitor ITO film resistivity optimization during annealing.

Reactive magnetron sputtering provides possibility of high-quality tin doped indium oxide In2O3:Sn (ITO) film deposition on a large substrates at low temperature. Although resistivity and transmittance of ITO films prepared by this technique greatly depend on the deposition parameters [1], which have to be optimized. Unique combination of the ITO properties is controlled by its electronic band structure parameters [2]; the latter can be characterized by optical methods. That is why, this work is focused on application of spectroscopic ellipsometry (SE) for probing of ITO layers.

The ITO films were grown by sputtering of metallic In (90%) - Sn (10%) alloy targets in atmosphere of Ar and O2 mixture by using pulsed dual magnetron system. Base pressure, Ar/O2 ratio and magnetron pulse duration have been varied during the deposition. The films were prepared on Si (100) covered with 500 nm SiO2 and soda lime glass substrates. Spectroscopic ellipsometry was applied within the wavelength range 300-1700 nm in combination with optical transmittance measurements. The spectral dependences of ellipsometric parameters were acquired in autoretarder mode. SE data were fitted simultaneously with transmittance data by using the model of rough graded layer [3] on substrate.

Such approach yielded ITO film thickness and roughness values, which were corroborated by profilometry and atomic force microscopy respectively. A significant variation in film deposition rate was observed only for experiments with different magnetron pulse duration. This parameter is minimal at 50 µs magnetron on-time, than it reaches maximum at 125 µs followed by further decrease at longer pulse durations. Such behavior can be related to changes in plasma density with variation of pulse length that was obtained by Langmuir probe measurements. The film lowest resistivity at high transmittance was achieved at pulse length 100-150 µs. The ITO optical constants were parameterized in Drude-Lorentz approach that permitted to obtain free electron parameters (plasma, wp, and relaxation, wt, frequencies) and interband transition characteristics. Vertical grading of optical constants through the film was quantified. During variation of base pressure, Ar/O2 ratio and pulse duration the minimum values of wt/wp^2 were reached at optimal deposition parameters that provided the lowest resistivity (3.2 mOhm·cm) of the film along with the high transmittance (0.84 for 180 nm thickness). For non optimal deposition parameters the behavior of wt/wp2 ratio qualitatively resembled resistivity dependence. Only in the vicinity of optimal deposition parameters resistivity is proportional to the ratio wt/wp^2 that points on the applicability of free electron approach in this case. For non optimal deposition parameters mechanisms of electric resistivity are more complex and require more detailed investigation of the film structure.

[1] R.B.H. Tahar, T. Ban, Y. Ohya, Y. Takahashi, J. Appl. Phys., 83 (1998) 2631
[2] O.N. Mryasov, A.J. Freeman, Phys. Rev. B, 64 (2001) 233111.
[3] R.A. Synowicki, Thin Solid Films 313-314 (1998) 394.

Investigations of processes involving actinides and bacteria in environments around nuclear waste repositories are needed for improvement of the scientific basis for performance of safety assessments. Sulfate reducing bacteria (SRB) are of special interest due to their ability to reduce many metals and actinides. Motamedi and Pedersen showed that SRB are frequently distributed in the deep granitic rock aquifers at the Äspö Hard Rock Laboratory (HRL, Sweden) [1]. The presented work is focussed on interactions of curium (III) and uranium (VI) with the strain Desulfovibrio äspöensis, DSM 10631T, recovered from the deep granitic groundwater at the Äspö site [1].
The interaction of D. äspöensis with Cm (III) was investigated by time-resolved laser fluorescence spectroscopy (TRLFS) in the trace concentration range. No evidences were found for changes in the oxidation state of Cm (III). At pH 3, no interaction between Cm (III) and bacteria was detected. With increasing pH, a surface complexation of Cm (III) occurs at the cell walls. The Cm (III)/bacteria surface complex is characterized by its emission spectrum (peak maximum at 600 nm) and its fluorescence emission lifetime (160 ± 15 µs).
80 % of the U (VI), solved initially (0.02 mM) in a liquid medium supplemented with lactate (10 mM) and bacterial biomass (1.10 g/L), was removed by the cells of D. äspöensis after 72 h of incubation at pH 5. Kinetic studies showed that the main amount of U (VI) was removed from the medium during the first 24 h. The microbial activity depended on pH, initial U (VI), and biomass concentration. By using X-ray absorption spectroscopy (XAS), we demonstrated that, in contrast to the above mentioned case with Cm (III), changes of the oxidation state of U (VI) in the precipitate formed by D. äspöensis occurred. The cellular localization of uranium removed from the medium was studied by using Transmission Electron Microscopy (TEM) and Electron-Disperse X-ray (EDX) analyses.

[1] Motamedi, M., Pedersen, K., Int. Syst. Bacteriol. 1998, 48, 311-315.

This work was funded by the BMWi under contract number: 02E9491.The authors are indebted for the use of the 248Cm to the U.S.. Department of Energy, Office of Basic Energy Sciences, through the transplutonium element production facilities at Oak Ridge National Laboratory which was made available as part of a collaboration between FZR and the Lawrence Berkeley National Laboratory (LBNL).

To protect the health of the population, knowledge is necessary about the transfer of radioactive heavy metals, like uranium, via the food chain soil-water-plant-animal-human. The overall process of uptake of heavy elements into plant tissues from contaminated soils is quantified using the soil-to-plant transfer factor (TF). The transfer factor of uranium for lupine and dandelion is in the range of 10-2 to 10-3. To obtain a more mechanistic understanding of the uptake of heavy metals in plants knowledge about the individual physical-chemical processes is needed. This study focuses on the determination of uranium speciation after uptake of uranium by plants (lupine, dandelions, lamb¢s lettuce). For the first time, laser-induced fluorescence spectroscopy and X-ray absorption spectroscopy were used to determine the chemical speciation of uranium in plants. Information on the spatial distribution of uranium in the plant was achieved by scanning electron microscopy, coupled with energy-dispersive X-ray microanalysis. Differences were detected between the uranium speciation in the initial solutions (hydrophonic and pore water of soil) and inside the plants. The oxidation state of uranium remained hexavalent after the uptake. The chemical speciation of uranium was identical in the roots, shoot axis, and leaves and was independent of the various investigated plants. First results are reported concerning the speciation of uranium in cell sap and solid cell components after separation. Spectroscopic data of relevant model compounds (e.g. sugar phosphates, inorganic phosphates, carboxylic acids, proteins) are compared with the uranium complexes in the different compartments of the plants.The results indicate that the uranium is predominantly bound to phosphoryl groups but in dependence on the experimental conditions the formation of uranium carboxylate complexes cannot be excluded.

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The sheet resistance and structural properties of high-fluence Si-implanted diamond were investigated. In order to minimize the radiation damage and to facilitate SiC formation the implantation was performed at 900 °C. All samples were subsequently annealed in an rf-heated furnace at 1500 °C for 10 minutes in order to remove defects and thermally unstable phases. X-ray diffraction, infrared absorption spectrometry and high-resolution cross-sectional transmission electron microscopy revealed the formation of a buried layer inside the implanted diamond, which contains SiC nanocrystallites. These SiC nanocrystals have a cubic structure and are nearly perfectly aligned with the diamond lattice. Raman spectroscopy was applied to analyze radiation-damage-induced graphitization in dependence on the implantation conditions. The sheet resistance of the samples was measured as function of temperature by four point probe technique in van-der-Pauw geometry. The decrease of the sheet resistance with increasing ion fluence unambiguously shows the influence of implantation-induced damage. The behavior of the sheet resistance can strongly be modified by additional nitrogen implantation The resulting higher conductivity is interpreted as partial incorporation of the nitrogen donor into the SiC nanocrystals. However, when the Si fluence exceeds a critical value of 5.3×1017 Si+cm-2 at 900 °C the diamond is irreversibly damaged and defect related conductivity dominates.

The mobility of actinides in the environment is determined by their speciation which is strongly influenced by their oxidation states. Humic acids (HA) influences the speciation of actinides by complexation. However, they have also significant redox properties which can affect the oxidation states of actinides and consequently their migration in the environment. Thus, it is very important to understand both the complexation and the redox properties of HA in natural systems.
In order to study the redox behavior of HA in more detail we synthesized HA model substances with distinct redox functionalities based on the oxidation of diphenolic compounds in the absence and presence of amino acids. These humic acid-like model substances are characterized by elemental compositions and structural elements that are comparable to natural HA. However, they show phenolic/acidic OH group contents that are higher than those of natural HA. For characterization of the redox properties of these synthetic products, their Fe(III) and ferricyanide redox capacities (RC) were determined at pH 3 and pH 9.2, respectively, and compared to that of purified natural HA from Aldrich. The synthetic products show RC that are up to a factor of 11 and 4 higher than that of Aldrich HA at pH 3 and pH 9.2, respectively. Additionally, we modified, i.e., etherified the phenolic OH groups of these HA by methylation with diazomethane. Applying these modified HA we verified the dominating role of phenolic OH groups in the redox behavior of these HA.
The synthesized HA model substances with distinct redox functionalities are applied to further improve the knowledge on the impact of HA on the redox stability of actinides in the environment. We study the redox stability of uranium(VI) complexes of these HA depending on pH. Uranium(IV) that is formed due to the redox process is spectroscopically determined both directly by laser-induced photoacoustic spectroscopy and indirectly in form of the uranium(IV) arsenazo(III) complex.

a-Si:H films prepared by plasma-enhanced CVD with 10% SiH4 in hydrogen have been studied concerning the effect of film thickness on the hydrogen concentration, interconnected void network and mechanical stress. The hydrogen concentration was determined by nuclear reaction analysis. The interconnected void network was studied by the method of ion exchange in glass substrate. The films were prepared at a substrate temperature in the range of 150 - 270°C. The results show that at the substrate temperature of 150°C the film structure develops as the void network decreases with the film thickness. At the substrate temperature of 270°C the film starts to grow with a dense structure and its structural improvement is manifested by the increase of the intrinsic compressive stress with the film thickness. The hydrogen concentration does not depend on the film thickness at any substrate temperature.

The interaction of the two chemical homologues (Cm (III) and Eu(III)) with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6±3)·105 L kg-1. Three different Cm(III) species have been identified: A non-fluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 nm and 620.9 nm and fluorescence emission lifetimes of 289 ± 11 µs and 1482 ± 200 µs, respectively. From the fluorescence lifetimes it was calculated that the two fluorescing Cm(III) species have one to two and no water molecules left in their first coordination sphere suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.
Key words : curium, europium, CSH, sorption, incorporation, TRLFS

A nuclear resonance fluorescence experiment with two highly efficient EUROBALL Cluster detectors has been performed on the Gamma-soft nucleus 194Pt. Dipole excitations were observed between 2 and 4 MeV excitation energy. They are tentatively interpreted as the main fragments of the scissors mode based on the measurec excitation strengths and a comparison to microscopic calculations in the framework of the quasiparticle random phase approximation (QRPA). The data indicate large differences to the neighbouring isotope 196Pt: a doublingof the observed dipole strength and a shift of the energy centroid by about 600 keV. None of the currently available models is able to reproduce these features consistently in both nuclei.

An investigation in the field of the crack initiation determination for Charpy size specimens was carried out. An extensive literature survey of published methods for the crack initiation was performed. Methods based on the stretch zone width measurement, blunting line, multiple gauge measurement, electric potential drop, compliance changing rate, acoustic emission, ultrasonic method and magnetic emission are discussed in the theoretical part of the report. Analytical methods for the critical J-integral evaluation were also taken into account, as well as the expressions for the J-integral calculation. On the basis of the theoretical survey suitable measurement methods were chosen and applied in the experimental programme to several different materials. Namely blunting line related methods, multiple gauge methods, electric potential drop and compliance changing rate methods were used. The initiation J-integrals were evaluated with use of wide range of evaluation procedures and compared together in order to find a reliable method for the crack initiation determination. There was not found a universal method for the crack initiation determination. The performance of the methods was varying in dependence on the investigated material, so the results enable to choose perspective method for considered case.

Low energy X-rays (Eph < 50 keV) are widely used in diagnostic radiology and radiotherapy. However, data on their relative biological effectiveness (RBE) are scarce. Of particular importance for risk estimation are the RBE value of X-rays in the range which is commonly used in mammography (10 - 30 keV). In the present study we have determined clonogenic survival after low-energy X-ray irradiation for 3 cell lines: primary human epidermal keratinocytes (HEKn), mouse fibroblasts (NIH/3T3) and Chinese hamster fibroblasts (V79). Experiments were performed with a 25 kV X-ray tube and compared to 200 kV X-rays as a reference. Compared to the effect of 200 kV X-rays, irradiation with 25 kV X-rays resulted in a decreased survival rate in the murine fibroblasts but not the human epithelial cell line. RBE value was calculated for 10 % surviving fraction. For HEKn cells, RBE was 1.33 ± 0.27, for NIH/3T3 cells 1.25 ± 0.07 and for V79 cells 1.10 ± 0.09. In conclusion, no consistently increased RBE was observed in the various cell lines. Nevertheless, a potential of increased cytogenetic changes has to be considered for risk estimation of low-energy X-rays.

Intersubband transitions in InP-based (Ga,In)As/(Al,In)As MQWs cover the wavelength range beyond 3.5 micron. Application of enhanced conduction band edge discontinuity allows for a reduced intersubband transition wavelength. This can be accomplished by replacing (Al,In)As by Al(As,Sb) barriers that can be grown lattice-matched to InP. (Ga,In)As/Al(As,Sb) MQWs were deposited by MBE and characterised using a combination of x-ray diffraction, photoluminescence and IR absorption measurements. Influence of well thickness and doping behaviour were systematically investigated. By
comparison with simplified theoretical calculations, the electronic band structure (interband and intersubband system) was deduced. Based on the corresponding results, the potential of (Ga,In)As/Al(As,Sb) MQWs for implementation in quantum cascade lasers will be discussed.

Mixed Oxide (MOX) fuel is usually considered as a solid solution formed by uranium and plutonium dioxides. Nevertheless, some physico-chemical properties of (U_1-y, Pu_y)O₂ samples manufactured under industrial conditions showed anomalies in the domain of plutonium contents ranging between 3 and 15 at.%. Cerium is commonly used as an inactive analogue of plutonium in preliminary studies on MOX fuels. Extended X-ray Absorption Fine Structure (EXAFS) measurements performed at the European Synchrotron Radiation Facility (ESRF) at the cerium and uranium edges on (U_1-y, Ce_y)O₂ samples are presented and discussed. They confirmed on an atomic scale the formation of an ideal solid solution for cerium concentrations ranging between 0 and 50 at.%.

The spatial coherence of hard X-rays provided by a bending magnet of the storage ring BESSY II was investigated performing Young's interference experiment. The interference pattern was created by the diffraction of two 2 µm pinholes drilled into a thin tantalum foil by focused ion sputtering. Using an energy-dispersive detector with an energy resolution of 200 eV the interference pattern were detected simultaneously between 5 keV < E < 16 keV scanning a 5 µm pinhole through the detector window. The set-up is suitable to characterise the coherence properties of the beamline in a simple manner, i.e. to deduce parameters as the effective source size, the coherence length and the visibility. For the present case the visibility is near 100% at 5 keV and decreases to 20% at 16 keV.

The spatial coherence of hard X-rays provided by a bending magnet of the storage ring BESSY II was investigated performing Young's interference experiment. The interference pattern was created by the diffraction of two 2 µm pinholes drilled into a thin tantalum foil by focused ion sputtering. Using an energy-dispersive detector with an energy resolution of 200 eV the interference pattern were detected simultaneously between 5 keV < E < 16 keV scanning a 5 µm pinhole through the detector window. The set-up is suitable to characterise the coherence properties of the beamline in a simple manner, i.e. to deduce parameters as the effective source size, the coherence length and the visibility. For the present case the visibility is near 100% at 5 keV and decreases to 20% at 16 keV.

Extended X-ray absorption fine structure (EXAFS) spectroscopy at the uranium L_III-edge was used for determining the structural environment of aqueous uranyl surbed onto montmorillonite. The study reveals that uranyl uptake at pH~5-~7 and at an initial uranyl concentration of 5x10^-5M takes place at amphoteric surface hydroxyl sites as inner-sphere complex. The measured bond distances sites between uranium and the equatorial oxygen atoms are in the range of 2.34 A the presence of a U-Al backscattering pair was determined. This backscattering pair indicates that the binding of the uranyl unit to amphoteric surface hydroxyl sites occurs preferred as a bidentate inner-sphere complex on aluminol groups.

Die nichtlineare Optik im THz Frequenzbereich ist weitgehend unerforscht [1], da hier keine abstimmbaren, intensiven Lichtquellen zur Verfügung stehen. Abstimmbare Freie-Elektronen Laser mit Emissionsfrequenzen im THz Bereich schließen diese Lücke. Wir haben Frequenzverdoppelung unterhalb der optischen Phononresonanz an dünnen GaAs Kristallen mit dem Freie-Elektronen Laser FELIX, Niederlande, durchfgeführt. Erstmals beobachten wir ein Maximum der nichtlinearen Suszeptibilität 2.Ordnung bei der halben Phononfrequenz (4,4 THz) und ein Minimum oberhalb dieser Frequenz (5,3 THz). Dieses Minimum basiert auf einem Vorzeichenwechsel der nichtlinearen Suszeptibilität bedingt durch konkurrierende elektronische und Gitterbeiträge. Ein Vergleich mit Berechnungen [2] zeigt, dass aus der Frequenz dieses Minimums die Beiträge höherer Ordnung des Gitterpotentials zur nichtlinearen Suszeptibilität quantitativ bestimmt werden können [3].

[1] siehe z. B. F. Keilmann, Infr. Phys. 31, 373 (1991).
[2] C. Flytzanis, Phys. Rev. B 6, 1264 (1972).
[3] T. Dekorsy et al. akzepziert zu Phys. Rev. Lett.

An overview of the research activities of the FIB group in the Research Centre
Rossendorf is given. More in detail the fabrication technology of alloy LMIS as well
as their characterization is discussed. The FIB system IMSA-100 is briefly
introduced and typical applications are presented: writing implantation of Co ions
into a heated Si target in order to create maskless sub-micron CoSi2 structures,
bombardment of semiconductor materials with different ions in a wide range of
current density, dose and temperature allows to study the damage creation and
dynamic annealing process.

Erbium silicide layers were grown epitaxially on Ge+ ion implanted Si. Epitaxy of ErSi2-x layers was achieved at temperature of 750 C.The layers are grown in the tetragonal phase.The growth of the silicide layers resulted in a drastic decrease of the dislocations in the SiGe layer accompanied by the accumulation of defects at the SiGe/ErSi2-x interface.A small redistribution of the Ge in the SiGe layer was also observed.

Solidified liquid metal ion sources (LMISs) operating with Au alloy wetted hair-pin emitters can be used as high-intensity electron point sources with nanometer dimension for electron field emission application. A nanoemitter tip on a solidified LMIS emitter can be formed by quenching during ion emission mode. I-V characteristics and the performance of the electron emitting LMIS are presented.

The study of trace-elements in archaeological metallic objects can provide important clues about the metal provenance and the involved manufacturing procedures, leading to important conclusions regarding the commercial, cultural and religious exchanges between the antique populations.
Ancient metallic materials are usually inhomogeneous on a scale of 20 microns or less: they contain remains of imperfect smelting, segregated phases in alloys, inclusions.
Due to their exceptional chemical stability, gold artefacts remain essentially unchanged during weathering and aging processes.
Several fragments of ancient gold objects coming from an Eneolithical treasury and from Pietroasa "Closca cu Puii Aur" ("The Golden Brood Hen with ITS Chickens") hoard, unearthed on Romanian territory and two Romanian native gold nuggets samples were analysed using micro-PIXE technique at the Rossendorf TANDETRON microbeam facility.
The purpose of the study was to clarify the metal provenance, establishing if the hypothesis of local gold holds. To reach this goal, trace elements (Cu, Te, Sn, Pb, Hg, As, Zr, Sb) and PEG (Platinum Group Elements) concentrations were determined.
The presence of inclusions (micrometeric size areas of compositions different from surroundings) was also checked. We found some Si, Ca, Fe ones on two Eneolithic samples, and a Ta-Cr one on sample from Pietroasa hoard. The measurements led to conclusions regarding the alluvial origin of the gold for the Eneolithical samples and gave some indications for the possible gold ore sources of Pietroasa treasury, confirming the heterogeneity of this treasury (the two analysed pieces belonged to different stylistic and compositional groups).
21 pieces of gold coins of KOSON type, considered the only kind of gold coins issued by the Daciens, were analysed using EDXRF and PAA (Proton Activation Analysis) methods at Bucharest Institute of Atomic Physics facilities. For EDXRF, three annular excitations sources - Pu 238 (30 mCi), Am 241 (50 mCi) and Am 241 (10 mCi, with nickel window for asorption of soft X-rays) and two X-ray detectors with Be window - a Si(Li) and an HPGe were used. For PAA, each coin was irradiated in vacuum for 5 hours at an incident proton energy of 11 MeV at a current of ca. 50 nA at the 8 MV FN High Voltage Bucharest Tandem and measured using a properly protected Ge(Li) gamma spectrometer. Three groups of coins of different compositions were found, corresponding to simple, complex and no monogram pieces. The gold of Koson coins is not a natural one (electrum) from present Romania's territory, but is similar to the gold of pseudo - Lysimachan staters. Some possible historical conclusions are discussed.

It is already known that the microstructure of a metallic alloy can be affected in a significant way due to the convection in the liquid phase during solidification. A time varying magnetic field can be applied to produce a flow field in the melt which influences the nucleation and growth processes. The aim of our research program is to find a strategy to refine the microstructure of castings by an optimal combination of magnetic field intensity, field frequency and cooling rate. Furthermore, the basic mechanisms controlling the solidification by magnetic fields are investigated.
A cylindrical crucible with a diameter of 50 mm was used to contain the Pb85wt%Sn alloy. A melt height of 60 mm was chosen. The container bottom is positioned on a water cooled copper chill allowing a directed solidification by a vertical heat flux. A rotating magnetic field was generated by an inductor system with 6 coils.
Local temperatures were determined during the solidification process using a set of thermocouples. Cooling curves measured at different locations inside the sample reveal the significant influence of the electromagnetic convection on the local heat transfer. Profiles of the melt velocity were obtained applying the ultrasonic Doppler method..
The Pb-85wt%Sn alloy shows a microstructure with primary tin-crystallites and eutectic. Specimens solidified without a rotating magnetic field showed a columnar dendritic microstructure which is orientated in heat flux direction. The tin crystallites and the eutectic are homogeneously distributed over the whole sample. If the alloy solidifies in a rotating magnetic field the microstructure changes. The shape of the dendrites changes from columnar to equiaxed in direction from the bottom to the top of the specimen and in the same direction the volume content of the eutectic increases.

By low dose ion implantation the magnetoresistance of LSMO is enhanced and the temperature of its maximum is shifted to lower values. At implantation of higher doses the LSMO films become semiconducting.

In the metastable solid solution Fe-15at.%Cr short range ordering (decomposition) was caused by irradiation at 723 K using Ar and Fe ions. The short range order parameter was evaluated from Moessbauer spectra. The short range order caused by the irradiation is much higher compared to the effect of only annealing at723 K for the same time without irradiation. The decomposition is not limited to the penetration depth of the ions but extends over the whole sample thickness of 30 µm. Therefore it is explained as due to radiation dynamic long range effects.

The complex formation of uranium(VI) with alpha-D-glucose 1-phosphate (C₆H₁₁O₆PO₃ ^2-, G1P) was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at pH 4 and potentiometric titration in the pH range from 3 to 10. Both measurements show the formation of a 1:1 complex at lower pH values. The formation constant of UO₂(C₆H₁₁O₆PO₃) was calculated from TRLFS measurements to be log beta₁₁ = 5.72 ± 0.12, and from potentiometric titration log beta₁₁ = 5.40 ± 0.25, respectively.
It was found by potentiometric titration that at higher pH values the complexation changes to a 1:2 complex. The stability constant for this complex was calculated to be log beta₁₂ = 8.96 ± 0.18.

The overall objective of the EC project "Humic Substances in Performance Assessment of Nuclear Waste Disposal: Actinide and Iodine Migration in the Far-Field" is the determination of the effect of humic substances on the actinide migration in natural systems to assess their impact on the long-term safety of radioactive waste repository sites and abandoned uranium mines. This task includes also the implementation of the present knowledge to real existing natural systems thereby verifying the correlation between important parameters, evaluating their environmental impact and finally, uncovering issues not addressed so far.
Uranium mining waste rock piles in the southern parts of the former East Germany represent a significant long-term environmental concern and liability. Although the uranium mines were decommissioned with the end of the uranium ore production in 1990, the legacy of forty-five years of uranium mining, such as abandoned mines, huge waste rock piles and mill tailings, represents a permanent reservoir and source of radioactive and non-radioactive contaminants. The discharge of radionuclides from the waste rock piles and contamination of the surrounding geosphere has to be minimized.
For the case study presented in this paper, the uranium mining waste rock pile no. 250 in Schlema/Alberoda (Saxony, Germany) was chosen. In many respects, this pile resembles other rock piles of this region. The site is characterized comprehensively with regard to composition and activity inventory of rock material and seepage water, uranium species occurring in the seepage water, TOC content and much more. Some important data of other uranium mining waste rock piles that were located in the vicinity of the rock pile no. 250 are also included in this study, especially the fulvic and humic acid content in the seepage water of rock piles and their loading with uranium. The data presented in this natural system study constitute the basis of performance assessment modeling.

Range distributions of carbon ions deposited onto tetrahedral amorphous carbon films at kinetic energies between 22 eV and 692 eV are measured utilizing high-resolution elastic recoil detection. These data are compared to range calculations based on binary collision approximation as well as to classical molecular dynamics simulations. Asymmetric range profiles, differences in mean ion ranges and increased range straggling compared to theories are attributed due to self diffusion during thermal spike as well as to intrinsic surface properties of the carbon samples which have to be considered in subplantation growth models.

The third report from the Project-Group ESRF-Beamline of the Forschungszentrum Rossendorf covers the period from January 2001 until December 2002. The Rossendorf BeamLine (ROBL) at the European Synchrotron Radiation Facility (ESRF) in Grenoble performed again well during this time - although we had major staff fluctuations, including two times a change in the project-management: Dr. W. Matz became head of the Technical Infrastructure at FZR, and Dr. T. Reich had been offered a professorship at the University of Mainz. We congratulate both of them. In the beamtime used by the FZR and collaborating institutes 77 different experiments were scheduled, while in the ESRF scheduled beamtime 21 experiments were performed by external groups. Additionally, a distinct amount of beamtime was devoted to commissioning of new equipment.

The report is organised in three main parts. The first part contains extendet contributions on results obtaines at ROBL. The second part gives an overview about the general experimental possibilities, scheduled experiments, publications, guests having visited ROBL with support of the EC, an staff information. Finally, the third part collects the experimental reports of the user groups received.

For the materials research experimental station of the Rossendorf beamline ROBL at the European Synchrotron Radiation Facility in Grenoble, France, a two magnetron sputter deposition chamber for in situ study of film growth by synchrotron X-ray diffraction and reflectivity was developed. It allows high-quality depositions of compound films and multilayers. Heteroepitaxial layer-by-layer growth of TiN on single crystal MgO(0 0 1) was observed by real-time specular X-ray reflectivity showing characteristic oscillations. The pseudomorphic growth was confirmed by high-resolution TEM micrographs. During growth on amorphous SiO2 on Si(0 0 1) substrates, the microstructural development of TiN films was studied in situ as a function of film thickness. With the deposition parameters chosen, a crossover was observed: grains with a (0 0 2) plane parallel to the film surface dominate at small thicknesses, while, at larger thicknesses, (1 1 1) grains dominate. Recrystallisation was identified as a mechanism that controls this texture development.

InGaAs/AlAs quantum wells (QWs) have the potential for the development of new devices based on intersubband transitions, such as near-infrared detectors, ultra-fast switches and light emitters that operate at the communication wavelength of 1.55 mm.However, the increased strain accommodation in the InGaAs/AlAs system considerably affects the band offsets of these QW structures and the performance of the appropriate devices. We report structural and optical characterization of InxGa1-xAs/AlAs/InyAl1-yAs (x ~ 0.7, y ~ 0.55) QW structures grown on InP substrates. In these structures, we utilize the high conduction band offset provided by AlAs. An increased In content in the wells and in the InyAl1-yAs layers helps to compensate the large AlAs tensile strain. Additionally, the smaller InGaAs band gap results in a shift of the first G-like well subband to lower energies relative to the X-minimum in the barrier layers even in very narrow wells. Intersubband absorption at wavelengths shorter than 2.0 mm is observed in thin single QWs. Also presented are spectra of asymmetric coupled QWs and short-period superlattices.

The surface hardness of the technically important alloy Ti–6Al–4V (wt.%) can be improved by nitrogen implantation. The structural mechanisms of hardening and of the stability of the improved hardness at elevated temperatures are studied. Ion implanted (II) and plasma immersion ion implanted (PII) samples were used. The formation of small TiN crystallites was detected in the as-implanted state, but only for the II samples a considerable surface hardness increase (factor 3) is observed. The in situ XRD experiments showed, that the TiN phase is stable up to temperatures of 650 °C for both types of implantation. At higher temperature Ti2N is formed which is stable up to 770 °C. ERDA results indicate a diffusion of nitrogen into the bulk material. The redistribution of N is responsible for the hardness changes: a slight decrease for II samples but an improvement by a factor of 2.5 for PII samples. The improvements/degradations of hardness and wear are discussed in correlation with the nitrogen depth distribution below the surface.

Au-ions were implanted into TiO2 single crystals with doses ranging from 2x1016Au+/cm2 to 6x1016Au+/cm2 at RT and 1000 K. At RT implanted samples were then thermally annealed at temperatures of 550 K to 1550 K. The Au-atoms precipitate to nanocrystals already during implantation at RT with an average particle size of 1.5 nm. HRTEM investigations revealed that the Au-nanocrystals, embedded in amorphous TiO2 regions, have a broad size and range distribution varying from large sizes in the near surface region to smaller sizes at larger depths. In the annealing process a reorientation of the Au-nanocrystals is observed, with the main effect of a decrease of the (111) peak and an increase of the (200)-peak in the XRD spectra. After annealing at 1000 K the particle size of the highly textured Au-implant was evaluated to ~ 6 nm; this means that during annealing the particles grow, leading to a partially coherent orientation in the disordered TiO2-matrix. Au implantation at RT performed through a metal mask with holes resulted in a narrow size distribution (2-6 nm) of the Au-nanocrystals in the near surface region.

The strong gettering of Cu atoms in single-crystal Si implanted with 3.5 MeV P+ ions was studied after thermal treatment and contamination with low amount of Cu impurity. Cu decorates the remaining damage generated by ion implantation. Three separate Cu gettering layers were detected by secondary ion mass spectrometry: at the main projected ion range, RP, below RP (RP/2 effect) and beyond RP (trans-RP effect). The defects acting as gettering centers at RP/2 and RP are implantation induced excess vacancies and excess interstitials, respectively. Cu profiles fit very well with depth distributions of excess vacancies and excess interstitials simulated by binary collision model for random and channeled ion incidence. The RP/2 and RP gettering layer are implantation induced, whereas the trans-RP gettering layer is formed by thermal treatment. The Cu accumulation in the trans-RP region increases with increasing temperature and/or with increasing annealing time. The RP/2 effect for P+ implantation was found to be significantly reduced in comparison with Si+ implantation. It completely disappears for higher P+ ion fluences. The obtained results are in agreement with the assumption that interstitials carried by P diffusion are the origin of Cu gettering in the trans-RP region.

The formation and evolution of radiation damage by ion bombardment consists of three stages: (i) atomic displacements during ballistic processes, (ii) formation of a (meta)stable defect structure after fast relaxation, and (iii) long-term thermally activated defect rearrangement, migration, recombination and reduction. The first two stages occur on very short time scales and are hardly accessible by available experimental methods. Atomistic computer simulations can contribute to a better understanding of these processes and of their microscopic mechanisms.
In this talk, a combined simulation method is employed to study a relatively simple case, the defect production by a single ion impact in silicon. Processes in the collision cascade with energy transfers above about 100 eV are treated by computer simulations based on the binary collision approximation (BCA). Classical molecular dynamics (MD) calculations are applied to consider processes in certain parts of the cascade which start with energy transfers less than about 100 eV. Detailed investigations are performed to study the temporal evolution of the defect structure until the beginning of the thermally activated phase, and to determine the damage morphology obtained after the fast relaxation. The influence of nuclear energy deposition and target temperature is discussed. The combination of BCA and MD methods allows the effective calculation of the total number and the depth distribution of different defect species (isolated vacancies and self-intersitials as well as more complex defects) formed on average per incident ion after the fast relaxation processes are finished. The procedure yields more realistic initial conditions for the simulation of post-implantation annealing than hitherto used.

In der Feinchemie- und Pharmaindustrie werden Chemikalien kleinerer Menge meistens durch diskontinuierlich geführte Batch-Prozesse hergestellt. Zur Unterstützung des Bedienungspersonals bei der schwierigen Prozessführung von Batch-Reaktoren (Rührkesselreaktoren) wurde ein Online-Monitoring-System (MoSys) entwickelt, das auf adaptiven Stoff- und Wärmebilanzen basiert. Die Industrieerprobung erfolgte im Rahmen eines entwickelten Batch-Informations-Management-Systems (BIMS), das in einem separaten Industrie-PC implementiert und über den Terminalbus in die vorhandene Automatisierungstechnik einer Mehrzweckanlage der Degussa AG eingebunden wurde. Die Betriebserfahrungen von zwei Produktionskampagnen zeigten, dass das BIMS/MoSys stabil und zuverlässig arbeitete und die Konzentrationsprofile gut mit den erwarteten Konzentrationsverläufen übereinstimmten.

Mit BIMS/MoSys sind folgende praktische Nutzanwendungen möglich:

• Einsparung einer chemischen Online-Prozessanalytik,
• Erweiterung und Archivierung des bestehenden Prozesswissens,
• Verbesserung der Produktqualität bei komplexen Batch-Prozessen,
• Optimierung der Prozessführung durch die genauere Ermittlung von Anlagen- und Prozess- Kenngrößen,
• Fehler- und Ursachenanalyse anhand der archivierten Batches,
• Rückverfolgbarkeit von Batches bei Problemen (z. B. Qualitätsbeanstandungen),
• Aufbau eines automatisierten Batch-Reports.

Darüber hinaus können unerwünschte Betriebszustände mit erhöhter Zwischenproduktakkumulation und verringerter Raum-Zeit-Ausbeute frühzeitig erkannt und dadurch rechtzeitig Gegenmaßnahmen eingeleitet werden, um größere Verluste zu vermeiden. Das auf adaptiven Stoff- und Wärmebilanzen basierende Online-Monitoring-System ist bei allen ausreichend exothermen ( oder endothermen) Semibatch-Prozessen einsetzbar, wenn geeignete Informationen in den Stoff- und Wärmebilanzen enthalten sind.

The FZR/IRC contributions are focussing on the interactions of actinides with indigenous bacteria in Äspö aquifer. We presenting the first results on interactions of the sulfate-reducing bacterium D. äspöensis (DSM 10631T) with uranium(VI). 80 % of the U(VI), solved initially in a concentration of 0.02 mM in a liquid medium supplemented with lactat (10 mM), was removed by the cells of this strain after 72 h of incubation at pH 5.

wird nachgereicht

Summary of the scientific activities of the institute in 2002 including selected highlight reports, short research contributions and an extended statistics overview.

wird nachgereicht

The grain and defect structure of submicrocrystalline and nanocrystalline nickel produced by equichannel angular pressing or by ball milling, respectively, has been studied by isochronal and isothermal annealing experiments, and Xray investigations. A detailed analysis of the thermal stability of the di.erent types of microstructures will be presented.

Bragg diffraction profiles were measured on single grains of different axial orientation in cyclically deformed Ni polycrystals. Diffraction profile parameters were determined and compared with results from profile measurements on fatigued single crystals, showing the same type of dislocation structure as the grains with corresponding axial orientation. Conclusions are drawn concerning the deformation processes in the grains taking into account the activated slip systems, the dislocation density and long-range residual strains.

Strong blue and violet photoluminescence (PL) and electroluminescence (EL) at room temperature has been achieved from thin SiO2 layers implanted with group IV elements. Thermally grown SiO2 .lms with thicknesses between 130 and 500 nm were implanted with Si, Ge or Sn ions followed by di.erent annealing procedures. Based on PL and PL excitation spectra we tentatively interpret the blue–violet PL as due to a T1- S0 transition of an oxygen deficiency center. The strong EL is well visible with the naked eye and reaches a power e.ciency of up to 5E-3 for Ge. Whereas the EL intensity shows a linear dependence on the injection current for Ge-rich layers, the shape of the EL spectrum remains unchanged. It was found that the I–V characteristics shift to lower applied electric fields with increasing implantation
fuence. Furthermore, it is assumed that the luminescence centers will be excited either by field ionization or by the scattering of hot electrons. Finally, the suitability of ion implanted silicon dioxide layers for optoelectronic applications is discussed.

Silicidation processes in nanoscale Ni and CoNi (5at.% Ni) layers on different silicon substrates were investigated using X-ray diffraction. The phase formation sequences as well as the formation and transition temperatures between 200 and 750°C were studied. The impact of different silicon substrates, i.e., polycrystalline Si and (100) oriented Si single-crystal substrates as well as the impact of different species of dopants (As, P) were analysed. The thermal range of the desired low resistance target phases NiSi and Co(0.95)Ni(0.05)Si(2) was determined. The temperatures for phase formation and phase transitions are significantly lowered on polycrystalline Silicon substrates.

Plasma immersion ion implantation of nitrogen in Si: Formation of SiO2,
Si3N4 and stressed layers under thermal and sputtering effects

Sponge-like and columnar porous silicon implanted with nitrogen by plasma immersion ion implantation (PIII)

Uranium mining waste piles are an enormous pool for heavy metal resistant bacteria. Many of these bacteria possess different mechanisms to detoxify metals, e.g. bioaccumulation, biotransformation, biomineralization or biosorption. The latter is of special interest for the development of bioremediation processes. We demonstrated that vegetative cells, spores and purified S-layer of Bacillus sphaericus JG-A12 which was recovered from a uranium mining waste pile near the town of Johanngeorgenstadt, Germany, bind selectively U, Cu, Pb, Al and Cd. In this work sol-gel techniques were used to immobilize cells, spores and stabilized S-layer of B. sphaericus JG-A12 in a porous silicate matrix. Processes of sorption and desorption of U and Cu by the produced biological ceramics (biocers) were investigated and compared with the binding properties of the single components. Localization of the bound metals was carried out using scanning electron microscopy and EDX analysis. Formed metal complexes were characterized by extended X-ray absorption fine structure spectroscopy (EXAFS). Our results demonstrate that spores followed by vegetative cells and the S-layer bind large amounts of U and Cu. The silicate matrix binds only small amounts of U and no Cu. The immobilization of the biocomponents in the bioceramics did not have any negative effect on the cells and S-layer but the metal binding capacity of the spores was strongly reduced. Binding capacity and binding kinetics of the biocers were positively influenced by adding water soluble additives as sorbitol or by freeze drying instead of air drying. The bound metals can be completely removed from the biocers by using aqueous citric acid what makes them reusable. EXAFS spectroscopy of the uranium complexes shows that uranium is bound via phosphate and carboxyl groups of the biocomponents as well as by the silicate and hydroxyl groups of the ceramic matrix. Because biocers possess high mechanical stability and metal binding capacity and are in addition reusable they are suitable for construction of intelligent filters for bioremediation.

The embrittlement of reactor pressure vessel steels is mainly effected by the neutron field. However, recently results have pointed out an additional or coupled effect of hydrogen. The aim was to investigate the influence of hydrogen on mechanical behaviour of different unirradiated reactor pressure vessel steels up to the working temperature in dependence on cathodic hydrogen charging conditions in correlation to chemical composition, microstructure, and hydrogen diffusivity and solubility. Diffusivity and solubility of hydrogen were determined by means of permeation measurements, thermodesorption measurements, and hot extraction. Small differences are mainly caused by the chemical composition of the steels. Higher copper and phosphorus contents do not yield an expected higher hydrogen uptake of the unirradiated steels. The mechanical properties were determined by slow tensile tests up to 250°C with simultaneously hydrogen charging in simulated reactor pressure water dependent on strain rate and charging conditions, and by impact tensile tests. The results of the mechanical tests and the corresponding fractographic analysis showed hardly an effect of hydrogen and no significant differences of the steels under the applied charging conditions. The loss of ductility decreases with increasing strain rate and increasing temperature. These results are the staring point for further investigations on irradiated samples.

Stationary and transient core calculations for a hypothetical boron dilution event have been carried out by the nodal code DYN3D. Two different two-group diffusion-parameter libraries, generated by the cell codes HELIOS and CASMO, have been used, in order to assess the influence of these data. Realistic core inlet boundary conditions have been applied using a validated semi-analytical coolant mixing model. The initial deborated-coolant-slug volumes, necessary for reaching recriticality in stationary calculations with both data libraries, differ by some 20 %. Differences are also observed in the height and time point of the power peak in transient calculations. The deviations between the applied data libraries are mainly due to different SCRAM reactivities and Doppler coefficients. Even when assuming a 36 m3 deborated slug, the core is brought back to subcriticality in all calculations.

AlN nanocrystalline layers and superstructures are used in the modern optoelectronic technology as reflecting mirrors in semiconductor lasers. In the present work the properties of AlN films prepared by sputtering methods from an AlN target in reactive Ar + N plasma were investigated. The characterisation was performed with HRTEM, SEM, glancing angle XRD and RBS methods. The present measurements confirmed the polycrystalline structure of AlN layers and enabled the evaluation of their grain size. The roughness and thickness of the layers were additionally determined by ellipsometric and profilometric measurements.

The structure and the elemental depth distributions of Y1Ba2Cu3O7-d (YBCO) and La0.7Sr0.3MnO3 (LSMO) were examined by q-2q XRD, and by 1.7 MeV 4He+ Rutherford Backscattering Spectrometry (RBS) in random and channeling geometry. The YBCO layers were magnetron sputtered, where the only one varying parameters were the oxygen pressure and the annealing time. The layers have high crystalline qualitiy and an almost sharp interface with the substrate as revealed by the analysis. It is shown that the oxygen content influences considerably not only the superconducting behavior, but also the lattice parameters and the cmin parameter (the minimum yield which is the ratio of aligned to random Rutherford backscattering spectra). We have found by high-precision RBS simulation, that independent on the film quality, a disordered interface region of 20 to 30 nm is present in all structures. As a complementary study we have performed also AES depth profiling.

We report here on ferromagnetic/superconductor FM/SC and SC/FM double layers deposited without a buffer layer between FM and SC. Thin films of La0.7Sr0.3MnO3 (LSMO) are used for the FM, and YBa2Cu3O7-x (YBCO) for the SC. Both films can grow crystalline on SrTiO3 (STO) or LaAlO3 (LAO) substrates in high temperature and in oxygen atmosphere conditions. Magnetic and transport measurements and X-ray diffraction analysis are used to characterise film quality and properties. It is shown that off-axis magnetron sputtering can be used for high-quality double layer deposition. A prerequisite for this is the suppression of the interdiffusion process. This is achieved by lowering the deposition temperature and shortening the deposition time for the top layer. Lattice relaxation for LSMO films deposited on LAO substrates is seen. It is demonstrated that post-deposition annealing or additional top layer deposition enlarges the relaxed part of the lower LSMO film. LSMO films are smooth and free of imperfections and the stress is partly relieved by the formation of misfit dislocations. For YBCO films, SEM, XRD, EDX and magnetisation characterisations show that film lattice relaxation starts when single-element-oxide crystals start to grow into the film. Many experiments give evidence of a critical thickness of about 30 nm of a strained layer, after which the top part of the YBCO film relaxes. Despite the small compositional deviation due to the interdiffusion, the YBCO/LSMO double films demonstrate high enough transport and magnetic properties to allow their application in the investigation of the injection of spin-polarised quasiparticles from FM to SC film. The critical current for YBCO film is Jc~0.7×106 A/cm2 if it is a bottom layer, and Jc~1.7×106 A/cm2 if YBCO is a top layer, whilst our optimal single-layer YBCO films have Jc~(2.5¯5)×106 A/cm2 at 77 K.

The OECD/NRC BWR Turbine Trip Benchmark was analysed by the codes DYN3D and the coupled code system ATHLET/DYN3D. Considering the calculations with given thermal-hydraulic boundary conditions of the core for the Exercise 2 of the benchmark the analyses were performed with the core model DYN3D. Concerning the modelling of the BWR core in the DYN3D code several simplifications and their influence on the results were investigated. The standard calculations with DYN3D were performed with 764 coolant channels (1 channel per fuel assembly), the assembly discontinuity factors (ADF) and the phase slip model of MOLOCHNIKOV. Comparisons were performed with the results obtained by calculations with 33 thermal-hydraulic channels, without the ADF and with the slip model of ZUBER-FINDLAY. It is shown that the influence on core-averaged values of the steady state and the transient is small. Considering local parameters the influence of the ADF or the reduced number of coolant channels is not negligible. For the calculations of Exercise 3 the DYN3D-model validated during the Exercise 2 calculations in combination with the ATHLET system model, developed at GRS for Exercise 1 has been used. Calculations were performed for the basic scenario as well as for all specified extreme versions. They were carried out using a modified version of the external coupling of the codes, the ?parallel? coupling. This coupling shows a stable performance at the low time step sizes, which are necessary for an appropriate description of the feedback during the transient. The influence of assumed failures of different relevant safety systems on the plant and the core behaviour was investigated in the calculations of the extreme scenarios. The calculations of Exercise 2 and 3 contribute to the validation of DYN3D and ATHLET/DYN3D for boiling water reactor systems.

With only a few exceptions, the numerical simulation of cosmic and laboratory hydromagnetic dynamos has been carried out in the framework of the differential equation method. However, the integral equation method is known to provide robust and accurate tools for the numerical solution of many problems in other fields of physics. The paper is intended to facilitate the use of integral equation solvers in dynamo theory. In concrete, the integral equation method is employed to solve the eigenvalue problem for a hydromagnetic dynamo model with a spherically symmetric, isotropic helical turbulence parameter alpha. Three examples of the function alpha(r) with steady and oscillatory solutions are considered. A convergence rate proportional to the inverse squared of the number of grid points is achieved. Based on this method, a convergence accelerating strategy is developed and the convergence rate is improved remarkably. Typically, quite accurate results can be obtained with a few tens of grid points.

At present, the GDT facility of the Budker Institute for Nuclear Physics Novosibirsk is being upgraded. The first stage of the upgrade is the Synthesised Hot Ion Plasmoid (SHIP) experiment. It aims, on the one hand, at the investigation of plasmas the parameters of which are expected to appear in the region of high neutron production in a GDT based fusion neutron source as proposed by the Budker Institute and, on the other hand, at the investigation of plasmas the parameters of which have never been achieved before in magnetic mirrors. The expected record values of plasma parameters and several peculiarities of the plasma offer a great field
for interesting investigations. In order to simulate the particle fields inside the GDT device and later in a GDT based neutron source an Integrated Transport Code System (ITCS) is being developed in collaboration between Forschungszentrum Rossendorf and Budker Institute. It consists of modules which allow the calculations of neutral gas, background plasma and of the fast ion component considering their mutual interactions. This contribution explains the concept of the SHIP experiment and presents the
results of first calculations by means of the ITCS modules.

A miniaturised ion selective electrode (ISE) for Cu2+ ions was developed, specially designed for application in a microfluidic system. The electrode was prepared on a silicon wafer substrate coated with a Cu deposit in the thickness range of 50 - 200 nm. The Cu layer was quantitatively converted into CuS by treatment in a sulphidic ambient. The chip electrode has a size of 5x5 mm2 and was mounted on a spacer chip coupled to the fluidic microcell using a chip clip technology. The coupling is liquid proof and reversible, permitting an easy exchange of the chip electrodes. The effective electrode area contacting the liquid of the microsystem flow channel amounts to about 4 mm2.

Sensitivity measurements were performed stationary and in the flow through cell. There was found a good Nernstian response of 29 mV/pCu between pCu 5 and 1 agreeing very well with reference measurements carried out with a commercial ISE.

The rapid response observed even in the dilutest solutions used, is related to the thin, non-porous structure of the CuS layer, minimizing diffusion effects during changing the test solutions. The adhesion of the sensitive CuS layer is different for the substrates Si, SiO2 and Si3N4 and depends on their history, roughness and evaporation conditions.

The first application of a Sonogashira cross-coupling reaction in ¹⁸F chemistry has been developed. The reaction was exemplified by the cross-coupling of terminal alkynes (ethynylcyclopentyl carbinol 6, 17alpha-ethynyl-3,17beta-estradiol 7 and 17alpha-ethynyl-3-methoxy-3,17beta-estradiol 8) with 4-[¹⁸F]fluoroiodobenzene. 4,4'-Diiododiaryliodonium salts were used as precursors for the synthesis of 4-[¹⁸F]fluoroiodobenzene, enabling the convenient access to 4-[¹⁸F]fluoroiodobenzene in 13-70 % yield using conventional heating or microwave activation. The Sonogashira cross-coupling of 4-[¹⁸F]fluoroiodobenzene with terminal alkynes gave the corresponding 4-[¹⁸F]fluorophenylethynyl-substituted compounds [¹⁸F]-9, [¹⁸F]-10 and [¹⁸F]-13 in yields up to 88% within 20 min starting from 4-[¹⁸F]fluoroiodobenzene.

The ¹⁸F-labelled amino acid derivative 3-O-methyl-6-[¹⁸F]fluoro-L-DOPA ([¹⁸F]OMFD) is a potential radiotracer to image tumour tissue using positron emission tomography. The precursor N-formyl-3-O-methyl-4-O-boc-6-trimethyl-stannyl-L-DOPA--ethyl ester enables the direct electrophilic radiofluorination by stereoselective destannylation. After partial hydrolysis, an optimized HPLC purification and sterile filtration the [¹⁸F]OMFD obtained with high radiochemical purity is ready for use. The total synthesis time is about 50 minutes and the radiochemical yield achieved is 20-25% (decay corrected, related to [¹⁸F]F₂). It was demonstrated that [¹⁸F]OMFD can be produced routinely and reliably for clinical use. [¹⁸F]FDOPA - preparation devices can be used with minor modifications.

On the basis of methods developed recently for square-fuel-assembly reactor cores, discontinuity factors for hexagonal VVER (Russian PWR) control absorbers and reflector nodes have been derived. Partial currents from heterogeneous multi-group transport calculations are used for the determination of the discontinuity factors. As shown by suitable benchmark calculations, the application of these quantities in the two-group nodal diffusion code DYN3D clearly improves the results of assembly-power predictions. The advantage of reflector diffusion parameters, including discontinuity factors, over conventional albedos has also been demonstrated.