Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

Aluminium titanium oxynitrides were studied as candidate materials for high temperature absorbers in solar selective coatings due to their excellent stability and their tuneable optical behaviour. A set of individual Al_yTi_1-y(O_xN_1-x) layers with different oxygen content was prepared by cathodic vacuum arc (CVA) deposition. The composition, morphology, phase structure and microstructure of the films were characterized by elastic recoil detection (ERD), scanning and transmission electron microscopy and X-ray diffraction. An fcc phase structure is found in a broad compositional range of Al_yTi_1-y(O_xN_1-x). Simultaneously, sample microstructure and morphology undergo systematic changes from a columnar growth to the development of a heterogeneous structure with spherical nanoparticle inclusions when the oxygen concentration is increased. The optical properties were determined by spectroscopic ellipsometry and UV–Vis–NIR and FTIR spectrophotometry. A comprehensive analysis of the film properties allowed an accurate modelling of the optical constants of the Al_yTi_1-y(O_xN_1-x) in the whole wavelength range of solar interest (from 190 nm to 25 µm). It points to a transition from metallic to dielectric behaviour with increasing oxygen content. Consequently, it is demonstrated that the optical properties of these Al_yTi_1-y(O_xN_1-x) deposited films can be controlled in a wide range from metallic to dielectric character by adjusting the oxygen concentration, opening a huge range of possibilities for the design of solar selective coatings (SSC) based on this material. Complete SSC, including a TiN layer as IR reflector, were designed by applying optical simulations, obtaining excellent optical selective properties of α=94.0% and ε_RT = 4.8%.

Phase transitions in carbon: nickel nanocomposite templates during diameter-selective CVD synthesis of SWCNTs were studied. While almost conserving their pre-defined diameter distribution, as-deposited Ni₃C nanoparticles transform into fcc-NiO during activation in low-pressure air atmosphere, and are reduced to a mixture of fcc-Ni and Ni₃C under nanotube growth conditions. The first phase transition leads to a substitutional replacement of the protective carbon matrix by a protective oxide layer. The second one reflects competing reduction processes of NiO. A mechanism for the complementary roles of carbon matrix and Ni species in the three-step CVD synthesis is proposed that includes nanoparticle immobilization, carbon delivery and catalysis of nanotube growth.

The solar cycle appears to be remarkably synchronized with the gravitational torques exerted by the tidally dominant planets Venus, Earth and Jupiter. Recently, a possible synchronization mechanism was proposed that relies on the intrinsic helicity oscillation of the current-driven Tayler instability which can be stoked by tidal-like perturbations with a period of 11.07 years. Inserted into a simple alpha-Omega dynamo model these resonantly excited helicity oscillations led to a 22.14 years dynamo cycle. Here, we assess various alternative mechanisms of synchronization. Specifically we study a simple time-delay model of Babcock–Leighton type dynamos and ask whether periodic changes of either the minimal amplitude for rising toroidal flux tubes or the Omega effect could eventually lead to synchronization. In contrast to the easy and robust synchronizability of Tayler–Spruit dynamo models, our answer for those Babcock–Leighton type models is less propitious.

Current Projects and Objectives at Helmholtz Institute Freiberg – Department of Metallurgy and Recycling

The separation of minerals has been a pressing issue in the last decades. One of the most common techniques to separate useful minerals from gangue minerals is Froth Flotation. Flotation is a relatively cheap and efficient process but the use of harmful chemicals and continuous decrease in ore quality due to the scarcity of high grade ores has motivated researchers to find alternative solutions to the standard flotation reagent scheme in order to make the process more efficient and environmentally friendly. Bioflotation has the potential of making the beneficiation of minerals more efficient and environmentally friendlier. Different bacteria and bacterial products have demonstrated to have prospective applications in bio flotation of different minerals (Behera and Mulaba-Bafubiandi, 2016). Halophilic bacteria are adapted to high salinity environments and other extreme conditions. Halophilic bacteria produce Extracellular Polymeric Substances (EPS) that aid them in the formation of biofilms and resist abrupt changes in salinity, pH, temperature and pressure. These EPS could have potential applications in flotation operations performed in sea water, such as the Copper-Molybdenum flotation operations in Chile. To date, there are no reports of halophilic bacteria been used in bio flotation experiments.
Halomonas boliviensis, Marinobacter spp, Halobacillus sp, Marinococcus sp and Halomonas eurihalina were studied to examine their potential as pyrite bio depressants, a gangue mineral common in Cu-Mo flotation. Micro flotation experiments using Hallimond tubes as well as flocculation, adsorption and Zeta potential experiments were performed in order to report the potential of these bacteria in the flotation process. In this study we will show the first results of using halophilic bacteria as Pyrite bio depressants, as well as an initial characterisation of the Extracellular Polymeric Substances excreted by these bacteria that could have an influence on the adsorption and mechanism by which these bacteria alter the surface of Pyrite.

Intrinsic and acquired resistances are major obstacles in cancer therapy. Genetic characterization is commonly used to identify predictive or prognostic biomarker signatures and potential cancer targets in samples from therapy-naïve patients. By far less common are such investigations to identify specific, predictive and/or prognostic gene signatures in patients or cancer cells refractory to a specific molecular-targeted intervention. This, however, might have a great value to foster the development of tailored, personalized cancer therapy. Based on our identification of a differential radiosensitization by single and combined β1 integrin (AIIB2) and EGFR (Cetuximab) targeting in more physiological, three-dimensional head and neck squamous cell carcinoma (HNSCC) cell cultures, we performed comparative whole exome sequencing, phosphoproteome analyses and RNAi knockdown screens in responder and non-responder cell lines. We found a higher rate of gene mutations with putative protein-changing characteristics in non-responders and different mutational profiles of responders and non-responders. These profiles allow stratification of HNSCC patients and identification of potential targets to address treatment resistance. Consecutively, pharmacological inhibition of mTOR and KEAP1 effectively diminished non-responder insusceptibility to β1 integrin and EGFR targeting for radiosensitization. Our data pinpoint the added value of genetic biomarker identification after selection for cancer subgroup responsiveness to targeted therapies.

Two natural mineral separates, labeled CoCal-N and CoFsp-N, have been prepared to serve as intercomparison material (ICM) for in situ-produced cosmogenic ³⁶Cl and natural chlorine (Clnat) analysis. The sample CoCal-N is derived from calcite crystals in a Namibian lag deposit, while the sample CoFsp-N is derived from a single crystal of alkali-feldspar from a Namibian pegmatite. The sample preparation took place at the University of Cologne and a rotating splitter was used to obtain homogeneous splits of both ICMs. Forty-five measurements of CoCal-N (between 1 and 16 per facility) and forty-four measurements of CoFsp-N (between 2 and 20 per facility) have been undertaken by ten target preparation laboratories measured by seven different AMS facilities. The internal laboratory scatter of the ³⁶Cl concentrations indicate no overdispersion for half of the laboratories and 3.9 to 7.3% (1σ) overdispersion for the others. We show that the CoCal-N and CoFsp-N splits are homogeneous regarding their ³⁶Cl and Cl_nat concentrations. The grand average (average calculated from the average of each laboratory) yields initial consensus ³⁶Cl concentrations of (3.74 ± 0.10) x 10⁶ at ³⁶Cl/g (CoCal-N) and (2.93 ± 0.07) x 10⁶ at ³⁶Cl/g (CoFsp-N) at 95% confidence intervals. The coefficient of variation is 5.1% and 4.2% for CoCal-N and CoFsp-N, respectively. The Cl_nat concentration corresponds to the lower and intermediate range of typical rock samples with 0.73 ± 0.18 μg/g in CoCal-N and 73.9 ± 6.8 μg/g in CoFsp-N. We discuss the most relevant points of the sample preparation and measurement and the chlorine concentration calculation to further approach intra-laboratory comparability. We propose to use continuous measurements of the ICMs to provide a valuable quality control for future determination of ³⁶Cl and Cl_nat concentrations.

As a cutting-edge type of photoinjectors, SRF gun is expected to provide a CW electron beam with high bunch charge and low emittance, which is highly demanded by the development of future FELs, ERLs and 4th/5th generation light sources. However, existing researches have not explored the full potential of SRF gun predicted by theory.

Status Report on Superconducting Rf Photoinjector application at ELBE

The Superconducting RF Photoinjector and its Present and Future Use at the ELBE Accelerator

The talk reports on operational aspects and experiences of photocathodes for the superconducting Rf photo injector at the ELBE accelerator

Liberation analysis on grinding products is a very important subject for application in respect of both mineralogical characteristics and beneficiation process relevant parameters. The Mineral Liberation Analyzer (MLA) combines a large specimen chamber automated Scanning Electron Microscope (SEM), multiple Energy Dispersive X-ray detectors (EDX) with automated quantitative mineralogy software. SEM-based automated mineralogy tools are essential in measuring parameters, such as modal mineralogy, mineral locking, mineral association, theoretical grade - recovery and mineral liberation.
Such quantitative information is fundamental to investigate and evaluate the mineral processing of ores. In this study carbonaceous apatite ore samples from Lao Cai deposit (Vietnam) was used. The petrographic, mineralogical and mineral liberation observations showed that the ore sample is quite
complex, containing carbonate impurities (dolomite and calcite) and having very fine intergrown texture. The separation of carbonate from apatite has been recognized as one of the most difficult subjects in mineral processing due to the similarities in their physiochemical properties.

Report on the Diagnostics for Beam Characterization of the ELBE SRF-Gun

Report on the beam transport simulation of the ELBE accelerator for injection with the SRF gun for THz, neutron and CBS applications.

The superconducting RF photoelectron gun at the ELBE accelerator facility is a high-repetition rate electron injector for CW operation and can provide high average current and high brightness electron beams. During commissioning and operating time different types of photocathodes, metallic (Cu, Mg) and semiconductors (Cs2Te), have been used. We present the preparation processes, properties as well as performance and operational experience of the cathodes in the SRF gun. Furthermore, specific issues like cathode cooling, multipacting, and dark current will be discussed.

In May 2014 the 1st superconducting photo injector (SRF gun) at HZDR was replaced by a new gun, featuring a new resonator and cryostat. The intention for this upgrade was to reach higher beam energy, higher bunch charge and lower emittance at the same time in order to serve user experiments at the superconducting CW accelerator ELBE. In our contribution we will report on the commissioning of the SRF gun by presenting a full set of RF performance results as well as detailed beam parameter measurements up to a bunch charge of 300 pC. Additionally, we will present the results of the first two user experiments (neutron and THz generation) that demonstrated the reliability of this gun concept.

An improved SRF gun (ELBE SRF Gun II) has been installed at the ELBE radiation center as an additional electron source since 2014. This new gun is able to produce up to 300 pC bunch charges in CW mode. This poster summarizes the latest results of user application with SRF Gun II

An SRF gun at the ELBE center has been operated with a magnesium cathode. Electron beams were produced with a maximum bunch charge of 200 pC and an emittance of 7.7 μm. Simulations have been conducted with ASTRA and Elegant for applying the SRF gun to ELBE user experiments, including neutron beam generation, positron beam generation, THz radiation and Compton backscattering experiment. Beam transport has been optimized to solve the best beam performance for these user stations at the bunch charge of 200 pC. Simulation results indicate that the SRF gun is potential to benefit the high bunch charge applications at ELBE.

The Mu2e electromagnetic calorimeter has to provide precise information on energy, time and position for ~100 MeV electrons. It is composed of 1348 un-doped CsI crystals, each coupled to two large area Silicon Photomultipliers (SiPMs). A modular and custom SiPM layout consisting of a 3 x 2 array of 6 x 6 mm UV-extended monolithic SiPMs has been developed to fulfill the Mu2e calorimeter requirements and a pre-production of 150 prototypes has been procured by three international firms (Hamamatsu, SensL and Advansid). A detailed quality assurance process has been carried out on this first batch of photosensors: the breakdown voltage, the gain, the quenching time, the dark current and the Photon Detection Efficiency (PDE) have been determined for each monolithic cell of each SiPMs array. One sample for each vendor has been exposed to a neutron fluency up to ~8.5 x 10^11 1 MeV (Si) eq. n/cm2 and a linear increase of the dark current up to tens of mA has been observed. Others 5 samples for each vendor have undergone an accelerated aging in order to verify a Mean Time To Failure (MTTF) higher than ~10^6 h.

Neutron total cross sections of natFe, 197Au and natW have been measured at the nELBE neutron time-of-flight facility in the energy range from 0.2 - 8 MeV with an uncertainty due to counting statistics of up to 2 % and a total uncertainty due to systematic effects of 1 %. The neutrons are produced with the superconducting electron accelerator ELBE using a liquid lead circuit as photo-neutron target. By periodical sample-in-sample-out measurements the transmission of the sample materials has been determined using a low-threshold plastic scintillation detector. The resulting effective total cross sections show good agreement with previously measured data that cover only part of the energy range available at nELBE. The results have also been compared to evaluated library files and recent calculations based on a dispersive coupled channel optical model potential.

In the course of evolution, nature has developed diverse strategies to avoid toxic effects of metals in the surrounding environment. Many organisms are able to bind metals to their surface via a variety of structurally diverse biomolecules carrying different functional groups. Because of the need for green and sustainable economic solutions, innovative biotechnological processes using biomolecules have become increasingly important.Biomolecules as sorbents are not only attractive for bioremediation, but also for the recovery of elements from recycling or mining. Currently, we are focusing on the development of new biosorbents based on short peptides for the selective recovery of valuable or toxic elements in complex process water streams such as Co, Ni, Ga or As and microparticles containing rare earth elements from fluorescent lamp powder. To select and identify these peptides we recently established Phage Surface Display Technology (PSD) as novel biotechnological platform in our group. Different adapted experimental setups for the peptide selection of each respective target material could be established and will be presented in detail. Specific and selectively metal binding peptides for particulate materials as well as for ionic species could be identified from commercially available phage libraries. These libraries contain a pool of genetically engineered phage of up to 10^9 different peptide motifs presented at their surface, which will be reduced in variability in an iterative biopanning process to capture the best binders. This contribution will give an insight into current research activities in our group focusing on PSD, introducing suitable spectroscopic techniques to characterize the metal-peptide complexes and discuss strategies for technical applications.

Session: Thin films type of contribution: Poster
Metal-induced crystallization with and without layer exchange (MIC w/o LE) is a method to decrease the crystallization temperature of amorphous group 14 elements (G14E) by up to several hundred degrees. In situ experiments are expected to provide new insights into thin film evolution and elementary process steps of MIC w/o LE and to improve existing models of this type of phase transformation. While MIC w/o LE has been widely studied for Si and Ge in contact with catalytic metals, there exist only a few studies for the crystallization of amorphous carbon. Therefore, in this contribution in situ Rutherford backscattering spectrometry (RBS), Raman spectroscopy and spectroscopic ellipsometry studies were performed during annealing of amorphous carbon/nickel (a-C/Ni) layer stacks at temperatures up to 750°C.
Due to its small lattice mismatch with the basal plane of graphite and high diffusivity of C atoms, Ni is a suitable catalyst for the growth of graphene and crystalline graphitic nanostructures. During the annealing of an a-C/Ni layer stack covalent bonds between the carbon atoms at the catalyst interface are weakened. Liberated carbon atoms can move along the interface and diffuse along the grain boundaries into the Ni layer towards the catalyst surface, where nucleation and grain growth of graphitic crystallites occur. Our in situ studies showed a change in the stacking sequence between C and Ni layers under defined experimental conditions. According to in situ Raman measurements, this mechanism occurs independent of the stacking sequence, while the velocity of the LE differs significantly. As observed in time and temperature resolved Raman spectra, the position of the G peak and the I(D)/I(G) ratio changed according to the Three-Stage-Model by Ferrari and Robertson, confirming the transformation of amorphous carbon to nc-graphite. With the in situ RBS measurements more insight into LE was given. Here peak positions of C and Ni were shifted, indicating a change of the energy of the scattered ions for both layers respectively and proving the combination of the observed graphitization process with LE during annealing. The thickness of the synthesized crystalline graphitic layer is controlled by the finite carbon source – the deposited a-C film, which is a decisive advantage of this process compared to CVD. It is demonstrated that the structure and the crystallite size of the metallic catalyst layer has a strong influence on the crystallite size and the quality of the graphitic film.
LE is potentially interesting for industrial applications, as it allows the formation of polycrystalline thin films of G14E at much lower temperatures - than during thermal annealing without the metallic catalyst. Depending on the initial stacking sequence, the crystalline graphitic film can be deposited on a suitable device-ready substrate or transferred to another substrate after the dissolution of the transition metal catalyst.

The contactless inductive flow tomography (CIFT) allows for reconstructing the mean flow structure of liquid metals by measuring the flow induced perturbations of one or more applied magnetic fields. These measurements are utilized to infer the flow field by solving a linear inverse problem using an appropriate regularization technique. We will give an overview of the application of CIFT to three models of continuous casting available at the Helmholtz-Zentrum Dresden – Rossendorf. These include a 1:8 and a 1:2 model of a slab casting mould as well as a 1:3 model of a cylindrical mould.

The Contactless Inductive Flow Tomography is a procedure that enables the reconstruction of the global three-dimensional flow structure of an electrically conducting fluid by measuring the flow induced magnetic flux density outside the melt and by subsequently solving the associated linear inverse problem. The accurate computation of the forward problem which is essential for the inversion represents the focal point of this investigation. The tomography procedure is described by a system of coupled integral equations where the integrals contain a singularity when a source point coincides with a field point. The contribution of a singular point to the value of the surface and volume integrals in the system is considered in detail. A significant improvement of the accuracy is achieved by applying higher order elements and by attributing special attention to the singularities inherent in the integral equations. The treatment of the singularities described in this investigation is similar to the procedure applied in the boundary element method. It represents a novelty in the Contactless Inductive Flow Tomography.

Geological mapping for mineral exploration using ground-based hyperspectral imaging in the thermal infrared

Local Lorentz force velocimetry (local LFV) is a contactless velocity measurement technique for liquid metals. Due to the relative movement between an electrically conductive fluid and a static applied magnetic field, eddy currents and a flow-braking Lorentz force are generated inside the metal melt. This force is proportional to the flow rate or to the local velocity, depending on the volume subset of the flow spanned by the magnetic field. By using small-size magnets, a localized magnetic field distribution is achieved allowing a local velocity assessment in the region adjacent to the wall. In the present study, we describe a numerical model of our experiments at a continuous caster model where the working fluid is GaInSn in eutectic composition. Our main goal is to demonstrate that this electromagnetic technique can be applied to measure vorticity distributions, i.e. to resolve velocity gradients as well. Our results show that by using a cross-shaped magnet system, the magnitude of the torque perpendicular to the surface of the mold significantly increases improving its measurement in a liquid metal flow. According to our numerical model, this torque correlates with the vorticity of the velocity in this direction. Before validating our numerical predictions, an electromagnetic dry calibration of the measurement system composed of a multicomponent force and torque sensor and a cross-shaped magnet was done using a rotating disk made of aluminum. The sensor is able to measure simultaneously all three components of force and torque, respectively. This calibration step cannot be avoided and it is used for an accurate definition of the center of the magnet with respect to the sensor’s coordinate system for torque measurements. Finally, we present the results of the experiments at the mini-LIMMCAST facility showing a good agreement with the numerical model.

Lorentz force velocimetry (LFV) is a contactless velocity measurement technique for electrically conducting fluids. When a liquid metal or a molten glass flows through an externally applied magnetic field, eddy currents and a flow-braking force are generated inside the liquid. This force is proportional to the velocity or flow rate of the fluid and, due to Newton's third law, a force of the same magnitude but in opposite direction acts on the source of the applied magnetic field which in our case are permanent magnets. According to Ohm's law for moving conductors at low magnetic Reynolds numbers, an electric potential is induced which ensures charge conservation. In this paper, we analyze the contribution of the induced electric potential to the total Lorentz force by considering two different scenarios: conducting walls of finite thickness and aspect ratio variation of the cross-section of the flow. In both the cases, the force component generated by the electric potential is always in the opposite direction to the total Lorentz force. This force component is sensitive to the electric boundary conditions of the flow of which insulating and perfectly conducting walls are the two limiting cases. In the latter case, the overall electric resistance of the system is minimized, resulting in a considerable increase in the measured Lorentz force. Additionally, this force originating from the electric potential also decays when the aspect ratio of the cross-section of the flow is changed. Hence, the sensitivity of the measurement technique is enhanced by either increasing wall conductivity or optimizing the aspect ratio of the cross-section of the flow.

A dedicated particle free UHV photocathode plug transfer chain from the preparation system to the SRF-Photoinjector was set up and commissioned at HZB for the bERLinPro project. The plug handling system was designed in collaboration with the ELBE team at HZDR, where the same transfer chain is in commissioning phase. In the future the exchange of photocathodes between the laboratories offers the possibility to test different types of photocathodes in different SRF-photoinjectors.

To improve the quality of photocathodes is one of the critical issues in enhancing the stability and reliability of photo-injector systems. Presently the primary choice is to use metallic photocathodes for the ELBE SRF Gun II to reduce the risk of contamination of the superconducting cavity. Magnesium has a low work function (3.6 eV) and shows high quantum efficiency (QE) up to 0.3 % after laser cleaning. The SRF Gun II with an Mg photocathode has successfully provided electron beam for ELBE users. However, the present cleaning process with a high intensity laser (activation) is time consuming and generates unwanted surface roughness. This paper presents the investigation of alternative surface cleaning procedures, such as thermal treatment. The QE and topography of Mg samples after treatment are reported.

Chemical composition, strain, structural polytypism and stacking faults in semiconductor nanostructures can be described quantitatively by high-resolution X-ray diffraction. It is a non-destructive technique that is suitable for the characterization of epitaxial nanostructures on their original substrates. The extracted information can be a valuable contribution to the understanding of the growth and strain relaxation mechanisms, which in turn are essential elements for tailoring the electronic properties in functional devices. Beamline P08 at PETRA III, Hamburg, offers a well-functioning high-resolution X-ray diffraction setup for the characterization of nanowire ensembles. Moreover, a newly developed configuration with a nano-focused beam is operational and can be used for the investigation of individual nanostructures.
The strengths of our setup have been tested in the characterization of GaAs/In_xGa_1-xAs core/shell nanowires. The nanowires were grown vertically on Si(111) substrates by molecular beam epitaxy (at HZDR). A set of samples with different shell thicknesses (5-80 nm) but the same In concentration (x≈0.20) and the same core diameter (25 nm) has been characterized. The measured in-plane and out-of-plane lattice constants as a function of the shell thickness suggest that the shell grew coherently around the core even for the thickest shell, the thickness of which is well beyond the critical value for planar In_0.2Ga_0.8As layers on GaAs. Furthermore, the tensile strain of the core due to the lattice mismatch with the shell increases with increasing the shell thickness up to 40nm, whereas the corresponding compressive strain of the shell decreases gradually to zero. All aforementioned results demonstrate the unique possibilities for strain engineering in core/shell nanowires.

Summary of the work done in 2016 and 2017 in Central-West Greenland and discussion of the results with the Karrat Zinc project team.

Positron emission tomography (PET) is an ideal method for tracing smallest amounts of radiolabelled substances propagating through widely impermeable material. It provides a means for experimental crossing of scales from molecular dimensions to the macroscale in particular in tight, heterogeneous, and complex materials. Characterization of transport properties of barrier material with this method benefits from its

• extremely high sensitivity („picomolar“),
• reasonable spatial resolution (around 1 mm),
• stability (up to years),
• direct comparability with and input for geochemical modelling.

The relaxation times of localized states of antimony donors in unstrained and strained germanium uniaxially compressed along the [111] crystallographic direction are measured at cryogenic temperatures. The measurements are carried out in a single-wavelength pump–probe setup using radiation from the Novosibirsk free electron laser (NovoFEL). The relaxation times in unstrained crystals depend on the temperature and excitation photon energy. Measurements in strained crystals are carried out under stress bar, in which case the ground-state wavefunction is formed by states belonging to a single valley in the germanium conduction band. It is shown that the application of uniaxial strain leads to an increase in the relaxation time, which is explained by a decrease in the number of relaxation channels.

Recently, ground-based hyperspectral imaging has come to the fore, supporting the arduous task of mapping near-vertical, difficult-to-access geological outcrops. The application of outcrop sensing within a range of one to several hundred meters, including geometric corrections and integration with accurate terrestrial laser scanning models, is already developing rapidly. However, there are only very few studies dealing with ground-based imaging of distant (i.e., in the range of several kilometres) targets such as mountain ridges, cliffs, and pit walls. In particular the extreme influence of atmospheric effects and topography-induced illumination differences have remained an unmet challenge on the spectral data. Those effects cannot be corrected by means of common correction tools for nadir satellite- or airborne data. Thus, this article presents an adapted workflow to overcome the challenges of long-range outcrop sensing, including straightforward atmospheric and topographic corrections. Using two datasets with different characteristics, we demonstrate the application of the workflow and highlight the importance of the presented corrections for a reliable geological interpretation. The achieved spectral mapping products are integrated with 3D photogrammetric data to create large-scale now-called “hyperclouds”, i.e. geometrically correct representations of the hyperspectral datacube. The presented workflow opens up a new range of application possibilities of hyperspectral imagery by significantly enlarging the scale of ground-based measurements.

The Dresden Felsenkeller ist a shallow-underground site featuring a rock overburden of 47 m which hosts a 5 MV Pelletron accelerator in tunnels VIII and IX. Using previous measurements in the lowbackground 𝛾-couting facility in tunnel IV as a benchmark, a FLUKA simulation has been developed to predict the neutron flux in tunnels VIII and IX. The simulation results provide insight into local neutron field inhomogenities caused by the measurement environment itself.

Hyperspectral long-wave infrared imaging (LWIR HSI) adds a promising complement to visible, near infrared, and shortwave infrared (VNIR and SWIR) HSI data in the field of mineral mapping. It enables characterization of rock- forming minerals such as silicates and carbonates, which show no detectable or extremely weak features in VNIR and SWIR. In the last decades, there has been a steady increase of publications on satellite, aerial, and laboratory LWIR data. However, the application of LWIR HIS for ground- based, close-range remote sensing of vertical geological outcrops is sparsely researched and will be the focus of the current study. We present a workflow for acquisition, mosaicking, and radiometric correction of LWIR HSI data. We demonstrate the applicability of this workflow using a case study from a gravel quarry in Germany. Library spectra are used for spectral unmixing and mapping of the main lithological units, which are validated using sample X-ray diffraction (XRD) and thin section analysis as well as FTIR point spectrometer data.

A new underground ion accelerator with 5 MV acceleration potential is currently being readied for installation in the Dresden Felsenkeller. The Felsenkeller site consists of altogether nine mutually connected tunnels. It is shielded from cosmic radiation by a 45 m thick rock overburden, enabling uniquely sensitive experiments. In order to exclude any possible effect by the new accelerator in tunnel VIII on the existing low-background gamma-counting facility in tunnel IV, Monte Carlo simulations of neutron transport are being performed. A realistic neutron source field is developed, and the resulting additional neutron flux at the gamma-counting facility is modeled by FLUKA simulations. – Supported by NAVI (HGF VH-VI-417).

Geringe natürliche Hintergrundstrahlung ist für die Untersuchung von Brennprozessen in Sternen von hoher Bedeutung. Für mehrere Szenarien wurden detaillierte FLUKA durchgeführt um die zusätzliche Strahlungserzeugung durch den neuen 5 MV Pelletron Beschleuniger zu studieren - mit dem Ziel die benötigte Abschirmung zu optimieren.

Flue dusts from copper metallurgy are resources for base metals such as copper, zinc, tin or lead. However, there is also a potential for the recovery of strategic elements like indium. At the moment flue dusts are recirculated within the copper process, but residues are available from historic produc-tion processes.
Hydrometallurgical processes seem to be a promising method to recover the base and strategic met-als from these fine-grained flue dusts. In preparation for further processing, the secondary material was characterized by mineral liberation analysis (MLA) and electron probe micro analysis (EPMA). An iron- and zinc-rich spinel phase (Zn,Fe,Mn)(Fe,Mn)2O4 was detected as the main phase (76 wt.-%) in the flue dust. The chemical composition of the flue dust was analysed by X-ray fluo-rescence spectroscopy (XRF spectroscopy). Leaching by sulfuric acid leads to precipitation of lead sulphate and calcium sulphate, which remain in the residue. The level of some impurities in the solu-tion can be controlled.
This work focuses on the selective recovery of copper and indium by solvent extraction from the leaching solution. Preliminary synthetic solutions of copper, iron(III), zinc, indium and mixtures of them were used for the investigations. The influence of pH value, concentration of acidic extract-ants, extraction time, and phase ratio on the extraction of copper, iron(III), zinc, and indium were studied. The results of the selective extraction of copper in the presence of iron(III) will be present-ed.

A FLUKA simulation has been made to analyse the propagation of neutrons from the future Felsenkeller accelerator throughout the tunnel system of Felsenkeller. A neutron flux measurement with detectors loaned by the BELEN-collaboration has been performed to put the accelerator induced neutron flux into perspective with the natural neutron background. To deduce the neutron flux from the counting rates, FLUKA has been used to simulate the detector responses. The three measured locations in the existing γ-measurement facility in tunnel IV show different traits in their neutron spectra. Their cause has been analysed and the results had an impact on the construction planning of the new Felsenkeller laboratory in tunnels VIII and IX.

Vorstellung der Studiengänge der Fakultät 5 der TU Bergakademie Freiberg.

Die Trennung von Kupfer und Eisen durch Solventextraktion ist in der Metallurgie, speziell bei der Verarbeitung von Lösungen aus dem Laugungsprozess oxidischer Kupfererze, ein vielfältig untersuchtes Verfahren. Es wurden die Reaktionsisotherme für Kupfer, die Zeit- und Konzentrationsabhängigkeiten sowie die Trennung von Kupfer und Eisen bestimmt. Die ermittelten optimalen Parameter werden angewendet, um den Prozess auf eine gerührte 32-mm KÜHNI-Extraktionskolonne (bereitgestellt durch SULZER Chemtech AG) zu übertragen. Die Einbauten sind aus korrosionsfestem Kunststoff und die wässrige Phase wird als disperse Phase gefahren.

The study of stable stellar burning reactions in nuclear astrophysics requires the use of ion accelerators in a low-background setting underground. Currently, there is only one such laboratory, the LUNA 0.4 MV accelerator deep underground in Gran Sasso/Italy. Several higher-energy underground accelerators are under development worldwide, including a 5 MV Pelletron to be placed in the Felsenkeller underground laboratory in Dresden/Germany. The shielding requirements for underground accelerators, where the paramount concern is the background in neighbouring rare-event searches is reviewed. Detailed FLUKA simulations have been carried out to study several different operating scenarios of the new 5 MV Felsenkeller accelerator, with a focus on the side effects on an existing γ-counting facility in the same tunnel system. The results of the simulations and practical implications will be discussed.

The study of stable stellar burning reactions in nuclear astrophysics requires the use of ion accelerators in a low-background setting underground. Currently, there is only one such laboratory, the LUNA 0.4 MV accelerator deep underground in Gran Sasso/Italy. Several higher-energy underground accelerators are under development worldwide, including a 5 MV Pelletron to be placed in the Felsenkeller underground laboratory in Dresden/Germany. The shielding requirements for underground accelerators, where the paramount concern is the background in neighbouring rare-event searches is reviewed. Detailed FLUKA simulations have been carried out to study several different operating scenarios of the new 5 MV Felsenkeller accelerator, with a focus on the side effects on an existing γ-counting facility in the same tunnel system. The results of the simulations and practical implications will be discussed.

The results of X-ray photoelectron spectroscopy measurements (core levels and valence bands) of RFe₅Al₇ (R = Lu, Tm, Er, Ho, Dy, Tb, Gd) single crystals are presented in comparison with the results of bulk magnetization studies and electronic structure calculations. It is shown that the increase of the Curie temperature in RFe₅Al₇ from Tm to Gd is associated with an increase of the indirect R 4f - Fe 3d exchange interaction at the expense of the multiplicity 2S + 1 (statistical weight) in the ground state ^{2S + 1}L_J of R³⁺ ions. The nonmonotonic behavior of the ferrimagnetic compensation temperature, Tcomp, as well as the values of the spontaneous magnetic moment, Ms, and formation energy, E_form, of the 4fⁿ levels in R metals in a series from ErFe₅Al₇ to GdFe₅Al₇ are explained by the difference in the quantum numbers L, J and S of the ground state of R³⁺ ions, leading to a maximum value of T_comp, M_s and E_form for the Dycontaining compound. The electronic structure of Gd/LuFe₅Alsub>7 is calculated using the GGA+U approach, on the basis of which the physical mechanism and relative strength of the interatomic R-Fe and Al-Fe interactions are considered, and also the difference in the magnetic moments of iron atoms in different structural positions is explained.

The single electron transistor (SET) is considered a promising candidate to continue the revolution of information technology due to its very low energy consumption (~100 times less then common FET). The big challenge is the manufacturability of SETs working at room temperature (RT). This requires the fabrication of much smaller structures (<5nm) than present-day and even future (multi-E-beam or EUV) lithography can provide.

Here we propose an ion-beam-assisted, CMOS compatible fabrication process of SETs. To realize the controlled tunneling of single electrons we propose a nanopillar of a Si/SiO2/Si stack with a single Si quantum dot embedded in SiO2 and connected by tunnel junctions to Si electrodes, which makes the drain and source. For RT operation the quantum dot has to be smaller than 5nm and requires tunnel distances lower than 2nm. The size of this pillar needs to be in the range of 10-20nm.

In this presentation we show the simulation of a CMOS compatible process to fabricate this quantum dot by using ion beam mixing and self-assembly. Earlier projects proved already the reliability of dot formations using ion beam mixing technologies. Starting with a layerstack of Si/SiO2/Si, the ion beam irradiation by high energy Si+ ions causes mixing of the two Si/SiO2 interfaces what transforms the SiO2 layer into metastable SiOx (Figure 1). During subsequent heat treatment the mixed region of SiOx (<10nm2) separates into Si and SiO2, what leads to the formation of one single Si nanodot in the SiO2 layer (Figure 2). The irradiation simulations are done by TRIDYN and TRI3DYN program codes and the annealing by a self-developed Kinetic Monte Carlo program. We will present, how this process can be controlled using the ion beam irradiation values, geometrical sizes and the heat treatment parameters, so that it is yielding suitable conditions for application in hybrid SET-CMOS devices operating at RT.

This part of the work is being funded by the European Union’s Horizon 2020 research and innovation program under Grant Agreement No 688072 (Project IONS4SET).

A new software, “MLALookUP”, for the analysis of geometallurgical data is demonstrated. It provides advanced visualization, integration of data from multiple sources, virtual process emulation, and data comparison.
Advanced visualization includes modal mineralogy, element deportment, virtual sieving, recovery curves, grade curves, etc. for various processing models. In this way promising processing machines and reasonable property thresholds can be identified.
The software allows combining data from various sources: automated mineralogy (e.g. from Mineral Liberation Analysis (MLA)), mineralogical compositions (e.g. from X-Ray powder diffraction) and elemental compositions (e.g. from wet geochemistry).
MLALookUP also allows to virtually “process” the material by emulating various processing machines. The emulation can separate particles based on various properties like size, density, magnetic and shape properties, and surface liberation. In this way it can emulate various processes from classification to flotation. It can handle ideal property based separations as well as imperfect separations, with property dependent recovery probabilities. A simple milling model allows including comminution.
Various processing machines can be combined in a sequence to model the effect of complete processing plants. In this way we can predict recovery, grade and mass streams, before actual processing experiments are need. This allows to play with processing parameters and to define appropriate machines, separation parameters milling target sizes, and promising processing routes. As MLALookUP can compute approximate liberation and particle properties the geometallurgical properties of the material is taken into account during this virtual processing.
Finally the software allows comparing all the different datasets in parallel graphics. This e.g. allows comparing emulation result with experimental data, which might either be given as another MLA dataset or as compositional data from other sources.
It is intended to provide more accurate simulation methods in later versions of the software.

Extrinsic effects on Cr2O3 thin films are shown. Also a statistical method to evaluate AF domain pattern in an electric way is demonstrated.

MERAM based on Cr2O3/Pt is presented

Magnetoelectric and purely antiferromagnetic RAM is shown based on Cr2O3/Pt

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

We optimized the syntheses of α- and β-Bi₄I₄ and transferred the method to the very bismuth-rich iodides Bi₁₄I₄, Bi₁₆I₄, and Bi₁₈I. Phase-pure, microcrystalline powders of Bi_mI₄ (m = 4, 14, 18) can now by synthesized on a multigram scale. Conditions for the growth of single crystals of Bi₁₆I₄ and Bi₁₈I₄ were determined. The redetermination of the crystal structure of Bi₁₆I₄ hints at a stacking disorder or the presence of ¹͚[Bi_mI₄] ribbons with m = 14 and 18 among the dominant type along with m = 16. The electronic band structures for m = 14, 16, and 18 were calculated including spin-orbit coupling. They vary markedly with m and show numerous bands crossing the Fermi level, predicting a 3D-metallic behavior. Measurements of the electrical resistivity of a polycrystalline sample of Bi₁₄I₄ as well as polycrystalline and single-crystalline samples of Bi₁₈I₄ confirmed their metallic nature over the temperature range 300 K to 2 K. For BiI₄, a positive and strictly linear magnetoresistance at 2 K in static magnetic fields up to 14 T was observed, which could indicate a topologically nontrivial electronic state.

Periodically patterned metamaterials are known for exhibiting wave properties similar to the ones observed in electronic band structures in crystal lattices. In particular, periodic ferromagnetic (FM) materials, also known as magnonic crystals (MCs), are characterized by the presence of bands and bandgaps (BGs) at tunable frequencies in their spin-wave (SW) spectrum. While those frequencies typically cover the GHz-range, no fundamental reason prevents one from extending this range towards THz-frequencies, a regime of high importance in communication technologies. Recently, the fabrication of magnets hosting Dzyaloshinskii-Moriya interactions (DMIs) has been pursued with high interest since properties such as the stabilization of chiral spin textures and nonreciprocal SW propagation originate from this antisymmetric exchange interaction. In this context, to further engineer the band structure of MCs, we propose the implementation of MCs with periodic DMIs, which can be obtained, for instance, patterning periodic arrays of heavy metals (HMs) on top of an ultrathin FM film. We demonstrate through theoretical calculations and micromagnetic simulations that such systems exhibit a unique evolution of the standing SWs around the BGs in areas of the FM film that are in contact with the HM wires. We also predict the emergence of at SW bands and indirect magnonic gaps, and we show that these effects depend on the strength of the DMI. This study opens further pathways towards engineered metamaterials for SW-based devices.

The talk is covering the efforts of our group in the development of inhibitor-based radiotracers for the imaging of tumour-associated transglutaminase 2. After introducing the biological function of transglutaminase 2, the development of substrates for fluorimetric activity assays will be lined out. Major emphasis will be put on the synthesis, kinetic characterisation and in vitro pharmacokinetic profiling of acrylamide-based irreversible inhibitors. Finally, labelling of these compounds with fluorine-18 and initial results towards their radiopharmacological evaluation will be discussed.

Report on results and status of photocathode development and measurement in the EC project EuCARD2.

Sm1-xTbxPO4 solid solutions were synthesized and extensively characterized by powder X-ray diffraction, vibrational spectroscopy, and X-ray absorption spectroscopy. At ambient conditions solid solutions up to x = 0.75 crystallize in the monazite structure, whereas TbPO4 is isostructural to xenotime. For x = 0.8 a mixture of both polymorphs was obtained. Moreover, a phase with anhydrite structure was observed coexisting with xenotime, which was formed due to mechanical stress. Selected solid solutions were investigated at pressures up to 40 GPa using in situ high pressure synchrotron X-ray diffraction and in situ high pressure Raman spectroscopy. SmPO4 and Sm0.5Tb0.5PO4 monazites are (meta)stable up to the highest pressures studied here. TbPO4 xenotime was found to transform into the monazite structure at a pressure of about 10 GPa. The transformation of Sm0.2Tb0.8PO4 xenotime into the monazite polymorph commences already at about 3 GPa. This study describes the reversibility of the pressure-induced (Sm,Tb)PO4 xenotime-monazite transformation.

The development of an active, earth-abundant and inexpensive catalyst for oxygen evolution reaction (OER) is highly desirable but remains a great challenge. Here, by combining experiments and first-principles calculations, we demonstrate that MoS₂ quantum dots (MSQDs) are an efficient material for OER. We use a simple route for the synthesis of MSQDs from a single precursor in aqueous medium avoiding the formation of unwanted carbon quantum dots (CQDs). The as-synthesized MSQDs exhibit higher OER activity with the lower Tafel slope as compared to that for the state-of-the-art catalyst IrO₂/C. The potential cycling of the MSQDs activates the surface and improves the OER catalytic properties. The density functional theory calculations reveal that MSQD vertices are reactive and the vacancies at the edges also promote the reaction, which indicates that the small flakes with defects at the edges are efficient for OER. The presence of CQDs affects the adsorption of reaction intermediates and dramatically suppresses the OER performance of the MSQDs. Our theoretical and experimental findings provide important insights into the synthesis process of MSQDs and their catalytic properties and suggest promising routes to tailoring the performance of the catalysts for OER applications.

A Ga focused ion beam (FIB) is often used in transmission electron microscopy (TEM) analysis sample preparation. In case of a crystalline Si sample, an amorphous near-surface layer is formed by the FIB process. In order to optimize the FIB recipe by minimizing the amorphization, it is important to predict the amorphous layer thickness from simulation. Molecular Dynamics (MD) simulation has been used to describe the amorphization, however, it is limited by computational power for a realistic FIB process simulation. On the other hand, Binary Collision Approximation (BCA) simulation is able and has been used to simulate ion-solid interaction process at a realistic scale. In this study, a Point Defect Density approach is introduced to a dynamic BCA simulation, considering dynamic ion-solid interactions. We used this method to predict the c-Si amorphization caused by FIB milling on Si. To validate the method, dedicated TEM studies are performed. It shows that the amorphous layer thickness predicted by the numerical simulation is consistent with the experimental data. In summary, the thickness of the near-surface Si amorphization layer caused by FIB milling can be well predicted using the Point Defect Density approach within the dynamic BCA model.

A previously published formalism to derive nanosphere sputtering yields is corrected and refined.

This review summarizes recent abstracts to international meetings and international peer-reviewed publications on the potential variation of the RBE and its possible side-effects, and compares these with past publication on photon beam irradiation. Moreover, recent literature on how to deal with potential RBE variations and the resulting uncertainty during treatment planning as well as solutions to correlate dose and LET distributions to subsequent (magnetic resonance) imaging changes are presented. Finally, the current status on RBE measured in vitro and in vivo is reviewed and input given on how to bridge the existing gap between lab and clinic.

Background: Enhanced proliferative activity in head and neck squamous cell carcinoma (HNSCC) adversely affects outcome after (chemo)radiotherapy. 3’-deoxy-3’-[18F] fluorothymidine (18F-FLT) positron emission tomography (PET) can be used for quantifying tumour proliferation and its changes during therapy. In this study, we investigated the complementary prognostic value of sphericity and standard metrics in 18F-FLT PET images before and during (chemo)radiotherapy regarding 4-year disease-free survival (DFS).
Methods: 48 HNSCC patients treated with radiotherapy (n=32) or chemoradiotherapy (n=16) with curative intent, underwent 18F-FLT PET-CT scans before and in the second week of treatment. Patients were followed for a median of 52 months. Primary tumours were delineated using the Fuzzy Locally Adaptive Bayesian algorithm. The proliferative volumes were further characterized by extracting SUV, volume and sphericity. Prognostic value for disease-free survival (DFS) of features was assessed using Kaplan-Meier survival analysis.
Results: In univariate analysis, the per-treatment sphericity (p=0.02, HR=4.2 [1.3– 13.9]) and SUVmean (p=0.03, HR=4.1 [1.2 – 14.2]) were prognostic factors, whereas none of the pre-treatment features were significant. Reduction in SUVmax (p=0.04, HR=4 [1.1 – 15.1]) was also a prognostic factor, but reduction of proliferative tumour volume did not reach statistical significance. The best stratification of patients for DFS was achieved with the combination of the two per-treatment features SUVmean and sphericity (p<0.001, HR=6.7 [1.8 – 25]).
Conclusion: High sphericity combined with low mean 18F-FLT SUV during treatment were associated with better DFS. These results suggest the potential prognostic value of advanced tumour proliferative volume characterization from 18F-FLT PET in HNSCC that may be further explored in larger cohorts.

Strain distribution in GaAs/In_xGa_1-xAs core/shell nanowires grown by molecular beam epitaxy on Si(111) substrates

The core/shell nanowire (NW) geometry is suitable for the pseudomorphic growth of highly mismatched semiconductor heterostructures, where the shell thickness can exceed significantly the critical thickness in equivalent planar heterostructures. We have investigated the accommodation of misfit strain in self-catalyzed GaAs/(In,Ga)As core/shell NWs grown on Si (111) substrates by molecular beam epitaxy. The NWs have their axis along the [111] crystallographic direction, six {11 ̅0} sidewalls, and their crystal structure is predominantly zinc blende. For strain analysis, we used Raman scattering spectroscopy, transmission electron microscopy, X-ray diffraction and photoluminescence spectroscopy. Within a certain range of core/shell dimensions and shell composition, our findings reveal that the elastic energy in NWs without misfit dislocations can be confined exclusively inside the core, allowing for the shell to be strain-free. The experimental results are also compared with theoretical simulations of the strain (continuum elasticity theory) and phonon energy (density functional theory).

Various self-organized nanoscale surface patterns can be produced by low- and medium-energy ion beam irradiation [1], depending on the irradiation conditions. Hexagonally ordered dot or pit patterns, checkerboard patterns, as well as periodic ripple patterns oriented perpendicular or parallel to the ion beam direction are formed spontaneously during the continuous surface erosion by ion sputtering. On amorphous surfaces, the formation of these patterns results from an interplay of different roughening mechanisms, e.g. curvature dependent sputtering, ballistic mass redistribution, or altered surface stoichiometry on binary materials, and smoothing mechanisms, e.g. surface diffusion or surface viscous flow.

An additional surface instability arises above the recrystallization temperature of the material. In this case, ion induced bulk defects are dynamically annealed and amorphization is prevented. The diffusion of ion-induced vacancies and ad-atoms on the crystalline surface is now affected by the Ehrlich-Schwoebel (ES) barrier, i.e. an additional diffusion barrier to cross terrace steps. Vacancies and ad-atoms are trapped on terraces and can nucleate to form new extended pits or terraces, respectively [2].

For the mathematical description of the pattern formation and evolution in the reverse epitaxy regime, a continuum equation can be used which combines the ballistic effects of ion irradiation and effective diffusion currents due to the ES barrier on the crystalline surface. By comparison with experimental studies of pattern formation on Ge and GaAs surfaces at different angles and temperatures, we will show that the pattern evolution is determined by the surface instability due to the ES barrier, surface diffusion, and ballistic effects of ion irradiation.

[1] A. Keller and S. Facsko, Materials 3, 4811 (2010).
[2] X. Ou, K.-H. Heinig, R. Hübner, J. Grenzer, X. Wang, M. Helm, J. Fassbender, and S. Facsko, Nanoscale 7, 18928 (2015).

Located in Goiás state of Brazil, Catalão I is a carbonatite complex that is part of the Alto Paranaíba Igneous Province. A niobium deposit in the complex, named Boa Vista, has been exploited for more than 40 years and is currently the world’s second largest niobium producer. The deposit is owned and operated by Niobrás, part of China Molybdenum Co.. Phosphates are also produced in the Catalão I complex at the Chapadão mine, an operation that is owned and operated by Copebrás, also part of China Molybdenum Co.. The phosphate production tailings are reprocessed at Boa Vista for recovering niobium as a by-product. Rare earth elements, albeit present in significant concentrations, are not recovered as by-products. This study provides quantiative mineralogical and microfabric data on the occurrence of rare earth minerals – and provides constraints for concentration of rare earth elements during current niobium beneficiation routes at the Tailings plant. Nine samples from different stages of the process were taken and characterized by Mineral Liberation Analyzer, X-ray powder diffraction and bulk rock chemistry. The recovery of rare earth elements in each of the tailing streams was quantified by mass balance. The results are used to identify the most suitable approach to recover REE as a by-product – without placing limitations on niobium production.
Monazite, the most common rare earth mineral identified in the feed to the Tailings Plant, occurs as Ce-rich and La-rich varieties that can be easily distinguished by SEM-based image analysis. Quartz, FeTi-oxides and several phosphate minerals are the main gangue minerals. The highest rare earth element content concentrations (1.75 wt.% TREO) and the greatest potential for REE processing are reported for the final flotation tailings stream. To place tentative economic constraints on REE recovery from the tailings material, an analogy to the Brown's Range deposit in Australia is drawn. Its technical flow sheet was used to estimate the cost for a hypothetical REE-production at Boa Vista. Parameters derived from SEM-based image analysis were used to model possible monazite recovery and concentrate grades. This exercise illustrates that a marketable REE concentrate could be obtained at Boa Vista, if the process could recover all particles with at least 60% of monazite on their surface. Applying CAPEX and OPEX values similar to that of Brown’s Range showed that such an operation would be profitable at current REE prices.

Low- and medium-energy ion beam irradiation can lead to various self-organized nanoscale surface patterns depending on the irradiation conditions [1]. If the sample temperature is below the material recrystallization temperature, the ion bombardment results in amorphization of the surface. On such amorphous surfaces, the formation of nanoscale patterns is driven by the interplay of different ion beam induced roughening and smoothing mechanisms: curvature dependent sputtering, ballistic mass redistribution or altered surface stoichiometry (on binary materials) are roughening the surface, while surface diffusion or surface viscous flow are smoothing it.

An additional surface instability arises above the recrystallization temperature of the material, when the surface remains crystalline during ion irradiation. In this case, the diffusion of ion-induced vacancies and ad-atoms on the crystalline surface is affected by the Ehrlich-Schwoebel (ES) barrier, i.e. an additional diffusion barrier to cross terrace steps. Vacancies and ad-atoms are thereby trapped on terraces and nucleate to form new extended pits or islands, respectively [2]. In molecular beam epitaxy mounds with different facets are formed due to the ES barrier. In ion-induced reverse epitaxy the additionally diffusing vacancies lead to different morphologies, like inverse pyramid and checkerboard patterns.

However, on Ge (001) surfaces irradiated at incidence angles greater than 50° mound patterns are formed and for angles greater than 75° the pattern turns into ripples. This transition from checkerboard over mound to ripple patterns in the reverse epitaxy regime can be described by a continuum equation which combines the ballistic effects of ion irradiation and the effective diffusion currents due to the ES barrier on the crystalline surface.

[1] A. Keller and S. Facsko, Materials 3, 4811 (2010).
[2] X. Ou, A. Keller, M. Helm, J. Fassbender, and S. Facsko, Phys. Rev. Lett. 111, 016101 (2013).

A geometallurgical study of the rare earth mineralogy and microfabric relations was undertaken at the Catalão I deposit, Chapadão mine, Goiás/Brazil. At Catalão I a carbonatite and its lateritic cap have been exploited for more than 40 years; being the world’s second largest niobium deposit and producer. The study was undertaken to assess the technical possibility and feasibility to recover rare earth minerals as a by-product of niobium production. For this purpose, nine samples were collected from different stages of the beneficiation process in the so-called Tailings Plant. Mineral Liberation Analyzer (MLA), X-ray powder diffraction and bulk rock chemistry were used to characterize these samples for their processing properties. The recovery of REE in each of the tailing streams was quantified by mass balance. The results were used to identify the most suitable approach to recover REE as a by-product – without placing constraints on niobium production.

Monazite is the dominant REE mineral in the feed to the Tailings Plant; this feed heralds from the exploitation of lateritic weathering residues. Quartz, FeTi-oxides and phosphate minerals are the main gangue minerals. The highest REE contents are reported in the final flotation tailings stream (1.75 wt.% TREO), with monazite-bearing particles in a size range suitable for further processing (10-120 µm size range). Yet, liberation of monazite in this particle size fraction is rather poor. By seeking an analogy to the Brown's Range deposit in Australia, a tentative economic assessment is attempted for REE production at Chapadão. For this purpose, parameters derived from MLA were used to model possible monazite recovery and concentrate grades. This assessment illustrates that a marketable REE concentrate may be obtained as a by-product at Chapadão even at current REE prices.

Compound semiconductors are versatile materials due to the possibility to tailor their (opto)electronic properties by selecting their composition appropriately. When grown heteroepitaxially, though, this possibility is constrained by the lattice mismatch with the substrate. In_xGa_1-xAs is a good example because it can have, depending on x, a suitable direct optical band gap for optoelectronic applications in the infrared (e.g. telecommunication wavelengths) or high electron mobility for high-speed transistors. However, the practical choices of x are limited by the available substrates, typically GaAs for low x or InP for x≈0.53.
Nanowires are a promising alternative for the realization of epitaxial heterostructures with high lattice mismatch due to their unique geometry and high surface-to-volume ratio. In addition, the possibility of monolithic integration in Si-CMOS platforms adds to their technological significance. In this work, we have investigated the growth of free-standing GaAs/In_xGa_1-xAs core/shell nanowires on Si(111) substrates by molecular beam epitaxy and the accommodation of lattice mismatch therein. Specifically, we have concentrated on highly lattice mismatched heterostructures (x=0.20-0.80) and very thin cores (diameter < 25 nm).
Self-catalyzed growth of very thin GaAs core nanowires with a sufficiently low number density (to avoid beam shadowing during the shell growth) was possible on native-oxide/Si(111) substrates, after an in situ treatment of the latter with Ga droplets. This resulted in zinc blende nanowires with their axis along the [111] crystallographic direction and six {1-10} sidewalls. Subsequently, conformal overgrowth of the In_xGa_1-xAs shell was obtained only under kinetically limited growth conditions that suppressed mismatch-induced bending phenomena. The strain in the core and the shell was studied systematically as a function of the shell composition and thickness. To that end, we used Raman scattering spectroscopy, transmission electron microscopy and (synchrotron/lab source) X-ray diffraction, and compared the results with theoretical predictions based on continuum elasticity and density functional theories. All findings point to the existence of anisotropic tensile strain in the core that increases (as quantified by Raman measurements) with increasing the shell thickness, whereas the corresponding compressive strain in the shell decreases to zero. Our work demonstrates the opportunity to grow not only relaxed In_xGa_1-xAs shells with high structural quality (as adopted from the GaAs core) in a wide, if not the whole, compositional range, but also highly strained (tensile) GaAs cores with (opto)electronic properties that remain to be explored.

arious self-organized nanoscale surface patterns can be produced by low- and medium-energy ion beam irradiation [1], depending on the irradiation conditions. Hexagonally ordered dot or pit patterns, checkerboard patterns, as well as periodic ripple patterns oriented perpendicular or parallel to the ion beam direction are formed spontaneously during the continuous surface erosion by ion sputtering. On amorphous surfaces, the formation of these patterns results from an interplay of different roughening mechanisms, e.g. curvature dependent sputtering, ballistic mass redistribution, or altered surface stoichiometry on binary materials, and smoothing mechanisms, e.g. surface diffusion or surface viscous flow.
An additional surface instability arises above the recrystallization temperature of the material. In this case, ion induced bulk defects are dynamically annealed and amorphization is prevented. The diffusion of ion-induced vacancies and ad-atoms on the crystalline surface is now affected by the Ehrlich-Schwoebel (ES) barrier, i.e. an additional diffusion barrier to cross terrace steps. Vacancies and ad-atoms are trapped on terraces and can nucleate to form new extended pits or terraces, respectively [2].
For the description of the pattern formation and evolution in the reverse epitaxy regime, a continuum equation can be used which combines the ballistic effects of ion irradiation and effective diffusion currents due to the ES barrier on the crystalline surface. By comparison with experimental studies of pattern formation on Ge and GaAs surfaces at different angles and temperatures, we will show that the pattern evolution is determined by the combined action of surface instability due to the ES barrier, surface diffusion, and ballistic effects of ion irradiation.
[1] A. Keller and S. Facsko, Materials 3, 4811 (2010).
[2] X. Ou, K.-H. Heinig, R. Hübner, J. Grenzer, X. Wang, M. Helm, J. Fassbender, and S. Facsko, Nanoscale 7, 18928 (2015).

Zirconium di-oxide (ZrO2 , zirconia) receives nowadays a big attention because of a variety of advantageous properties which make zirconia-based materials useful in numerous fields of practice, in particular, in ceramic industry and other high-temperature applications. To make high-temperature phases of zirconia stabilised down to room temperature, doping of the host lattice by proper metal cations has to be usually performed. Nanopowders are currently focused on as starting substances for manufacturing ZrO2-based ceramics by sintering, because well-homogenised materials of a low porosity can be produced more easily. Nanometer-sized defects associated to grain boundaries (GBs) become then to play an enhanced role in nanopowders due to enlarged volume fraction of GBs. Positrons and positronium (Ps) atoms can serve as efficient probes of different structures encountered in particular stages of manufacturing ZrO2-based functional materials. In the present contribution, conventional positron and Ps lifetime measurements were carried out on a variety of zirconia-based nanopowders and ceramics obtained by sintering these nanopowders. Nanopowders studied were doped with various metal cations (Y3+, Cr3+, Ce4+, Mg2+) and differed also in thermal treatment prior sintering. Lifetime experiments were conducted in air or in vacuum and combined with Doppler broadening measurements using slow-positron beam and supplemented with X-ray diffraction (XRD) and mass-density (MD) measurements. In Figure, variability of the lifetime spectra observed is illustrated. In a range of lifetimes from a few ns to ≈ 70 ns, up to three individual lifetime components could be identified, see Figure, (a) and (b). Such observations unambiguously testified Ps formation with subsequent ortho-Ps annihilation. On the other hand, an absence of the ortho-Ps components was found in certain nanopowders giving thus an evidence of a strong Ps inhibition, see Figure, (c). Pore sizes were estimated using current models of correlation between observed ortho-Ps lifetime and pore size. Origins of pores will be discussed on the basis of the ortho-Ps data in combination with the results of slowpositron beam, XRD and MD measurements.

Nanostructured metals containing nano- and micro-cavities can be prepared by various methods. Morphology of cavities can be controlled by varying the parameters of preparation. This enables fabrication of nanostructured metals with properties tailored for particular applications, e.g. nanostructured metals containing fractal-like cavities with a wide size distribution are used as omnidirectional absorbers of light from the visible into the infrared spectral region. Positronium (Ps) is a non-destructive probe of nanoscopic cavities capable of precise determination of their size distribution. In conventional metals Ps does not form since any bound state of positron and electron is quickly destroyed by the screening of conduction electrons. However, a thermalized positron escaping from a metal through inner surface into a cavity may form Ps by picking an electron on the surface. This process was examined in the present work on nanostructured metals prepared three various methods: (i) thin films of black metals (Au and Al) evaporated in N2 atmosphere; (ii) nano-porous bulk Pd prepared by electrochemical etching of PdCo alloy; (iii) nanostructured Gd prepared by selective evaporation of Mg from MgGd alloy. Our investigations confirmed that Ps was formed in nanostructured metals. The the size distribution of nano-pores in the samples has been determined. The mechanism of Ps formation in these samples is discussed in the paper.

Smart membranes play a key role in different sensor applications, e.g. for drug and explosive detection. By tailoring the structure and properties of these membranes physical-chemical functionality can be added to the sensor. One way of modifying membranes is by particle irradiation with electrons or ions. Specifically, highly charged ions (HCI) carry a large amount of potential energy (the stored ionization energy) which is released when interacting with the membrane creating nanopores by a single HCI impact. In order to be able to control the ion induced modification, e.g. defining the pore size, the energy deposition in the membranes has to be determined.
For the interaction of HCI with thin membranes this is particularly interesting because the HCIs are still in a pre-equilibrium interaction regime for thicknesses below a few nm. Within 1 nm thick carbon nano membranes (CNMs) for instance, holes are produced by the passage of highly charged Xeq+ ions only above a threshold in the potential energy of the HCI which depends on the kinetic energy [1]. In order to study the stopping force of the HCIs in the membrane we examined the charge state and the energy loss of the Xeq+ ions after their passage through the CNM. Surprisingly, two distinct exit charge distributions were observed [2]. While some of the ions pass the membrane with almost no charge loss, other ions lose most of their charge. Apparently, the observed charge distribution reflects two different impact parameter regimes. The different impact parameter regimes are also connected to different energy losses: ions with large impact parameters are not stopped, whereas ions in close collisions exhibit high stopping force which is strongly dependent on the incident charge state.
[1] R.A. Wilhelm, E. Gruber, R. Ritter, R. Heller, A. Beyer, A. Turchanin, N. Klingner, R. Hübner, M. Stöger-Pollach, H. Vieker, G. Hlawacek, A. Gölzhäuser, S. Facsko, and F. Aumayr, 2D Mater. 2, 1 (2015).
[2] R.A. Wilhelm, E. Gruber, R. Ritter, R. Heller, S. Facsko, F. Aumayr, Phys. Rev. Lett. 112, 153201 (2014).

The pore size of spin-on coated ultra-low K (ULK) materials cured at 4500C for different times was studied by the pulsed slow positron beam (MePS) at ELBE/HZDR. To investigate the pore formation in cured porous spin-on dielectrics, the pore size as a function of positron implantation energy was obtained for samples with different curing times. Such a study is performed to understand the dielectric damage behaviour of ULK dielectrics for the integration in Back-End of Line (BEOL). MePS results revealed that the films contain open and closed pores with ~ 3 nm in diameter which was confirmed by capping the samples. The highest pore concentration is located beneath the surface in the 0.2 - 0.5 m range (We plan to carry out ellipsometric porosimetry and FTIR during this summer). Pseudomorphic transformation of porous glass-thin layers, with pores of 40 - 50 nm diameter and a relatively small surface area, to MCM-41 with ~4 nm pores, with a higher surface area, was studied by MePS. The small pore size of MCM-41 was successfully detected with an intensity growth with transformation degree but the large pores were not detected at all. To understand the disability of detecting the large pores by positron annihilation lifetime, we plan to perform SEM measurements in the same depth as that of the implanted positrons (0.005-2.4 m).
Additionally, the increase in the intensity of positronium lifetime, which correlates the small pores, as a function of positron implantation energy could reflect inner pore isolation or poor interconnectivity.

Porous spin-on glasses belong to ultra low-k (ULK) dielectrics and are promising candidates for integration in the semiconductor device fabrication technology. Their microstructure consists usually of interconnected pore networks distributed across the film rather than separated voids. The pore size and distribution are controllable to a large extent, however, the pore formation process itself is still not well understood. A dielectric damage during integration and material degradation of films with large porosity are still problematic issues. The first results on in-situ investigations of the pore formation during a curing process – a porogen removal by vacuum annealing will be presented. The main motivation is to obtain the insight into early stages of the pore formation and up to its full development. The in-situ annealing and Doppler Broadening – Positron Annihilation Spectroscopy (DB-PAS) measurements have been done on our Apparatus for In-situ Defect Analysis (AIDA) system [1], which is the end-station of the slow positrons beamline at HZDR. The comparison between preliminary ex-situ studies by means of DB-PAS [see Fig. 1], Positron Annihilation Lifetime Spectroscopy (PALS), and Fourier Transform Infrared Spectroscopy (FTIS) will be given.
In Fig. 1(a) it is shown that o-Ps emission increases with t, thus can be a probe of films porosity as long as they are capped. The curing time of 5-30min. is sufficient to fully develop the pore network [Fig. 1(b)]. Porosity development and distribution will be discussed for annealing temperatures in the 100-400°C range and varied annealing time.
[1] M.O. Liedke et al., Journal of Applied Physics 117, 163908 (2015).

Electronics has been dominated by silicon since half a century. Si will dominate electronics another decade, however its functionality might change from classical field-controlled currents through channels (the Field Effect Transistor FET) to quantum mechanical effects like field-controlled hopping of single electrons from a source to a drain via a quantum dot (the Single Electron Transistor SET). Due to single electron hopping, the SET is the champion of low-power consumption. This is very attractive for the expanding Internet of Things (IoT): more and more devices need batteries and plugs. Therefore, together with improved batteries, advanced computation and communication must be delivered at extremely low-power consumption. At very low temperatures, the perfect functionality of SETs has been proven for tiny metal dots [1] and larger Si islands [2]. However, large-scale use of SETs requires Room Temperature (RT) operation, which can be achieved with tiny Si dots (<4 nm) in SiO2, exactly located between source and drain with distances of ~1…2 nm allowing quantum mechanical tunneling. Manufacturability of such nanostructures is the roadblock for large-scale use of SETs. Lithography cannot deliver the feature sizes of 1…3 nm required for RT operation. Therefore, there are currently intense studies to fulfill these requirements by self-organization processes. Convincing proof of concepts have been reported [see, e.g., 3] on room temperature operation of silicon based SETs. However, the self-organization processes developed so far are not reliable enough for large-scale integration.
The ion beam technique is a well-established technology in microelectronics used for doping and amorphization of semiconductors and even for ion beam synthesis of buried layers. The parameters of ion beam processing like ion flux, fluence and energy as well as the temperature and time of the subsequent thermal treatment are very well controllable. Therefore we searched for a self-organization process based on ion irradiation which overcomes the bottleneck of manufacturability of SETs working at room temperature.
Thus, in the framework of an international project funded by the European Commission [4], we develop an ion-assisted, CMOS-compatible process [4] which will provide both (i) self-assembly of a single Si dot and (ii) its self-alignment with source and drain.
Based on our knowledge of ion implantation [5,6] and irradiation [7] induced phase separation and Ostwald ripening processes as well as ion-assisted fabrication of non-volatile nanocluster memories [8], we concluded by computer simulations that phase separation of tiny, metastable SiOx volumes (<103 nm3) will transiently lead to a single Si nanodot in SiO2 (see Fig.2).
The tiny, metastable SiOx volume is formed by ion beam mixing of a bulk Si/SiO2/a-Si layer stack. In order to get the very small SiOx volume necessary for single dot formation, two approaches are used: (i) point-like Ne+ irradiation for fundamental studies, and (ii) broad beam Si+ irradiation of nanopillars for the device fabrication (see Fig. 3).
For both approaches, the predictive computer simulations use for the dynamical 3D ion beam mixing the recently developed program TRI3DYN [9]. TRI3DYN provides the initial conditions for phase separation and coarsening processes simulated (see, e.g. Fig. 2) with the 3D kinetic Monte Carlo program 3DkMC [6].
First results of our studies with the Helium Ion Microscope are shown in Figs. 4 and 5. The ion beam mixing of the SiO2 layer as imaged by EFTEM agrees nicely with that predicted by TRI3DYN simulations. Using this mixing profile as input for 3DkMC simulations, a single Si nanocluster is formed (Fig. 4). Although it appears to be extremely difficult to image a single Si nanodot of 2…3 nm diameter embedded in SiO2 in a ~50 nm thick TEM lamella, Fig 5 proves that after annealing such a single cluster can be formed. The next activities will be focused on the single Si nanodot fabrication in Si nanopillars and the optimization of this process for RT-SET fabrication.

This work has been funded by the European Union’s Horizon 2020 research and innovation program under grant agreement No 688072.

1. K. Maeda et al., ACS Nano (2012) 2798.
2. S. Ihara et al., Appl. Phys. Lett. 107 (2015) 13102. SET in SOI
3. V. Deshpande et al., Proc. of the IEDM12-Conf. (2012) 195.
4. Research Project IONS4SET funded by the European Commission
5. M. Strobel et al., NIM B147 (1999) 343.
6. M. Strobel, K.-H. Heinig, W. Möller, Phys. Rev. B64 (2001) 245422.
7. K.H. Heinig, T. Müller, B. Schmidt, M. Strobel, W. Möller, Appl. Phys. A77 (2003) 17.
8. T. Mueller et al., Appl .Phys. Lett. 81 (2002) 3049; ibid 85 (2004) 2373.
9. W. Möller, NIM B322 (2014) 23.

Titanium readily absorbs hydrogen and undergoes phase transition into the hydride phase (TiH2). In the hydride phase Ti is able to absorb the hydrogen concentration as high as 1.4 wt.%. These properties make Ti and Ti-based alloys attractive for hydrogen storage applications. Hydrogen absorption in titanium matrix may introduce open volume defects since the volume of TiH2 phase exceeds that of titanium matrix. Absorbed hydrogen may segregate at these defects forming defect-hydrogen complexes.
In the present work positron annihilation spectroscopy was employed for characterization of hydrogen-induced defects in titanium. Defects created by hydrogen loading from the gas phase were compared with those introduced by electrochemical hydrogen charging. In general hydrogen loading introduces a high density of dislocations and vacancy clusters created by agglomeration of hydrogen-induced vacancies. The mean size of vacancy clusters depends on the hydrogen absorption temperature.
Thermal stability of hydrogen absorbed in titanium and recovery of hydrogen-induced defects were studied by positron lifetime spectroscopy combined with in-situ X-ray diffraction and thermal desorption spectroscopy. Fig. 1 shows the temperature dependence of positron lifetimes and relative intensities of individual components for hydrogen gas loaded titanium. The decomposition of TiH2 phase is accompanied with introduction of additional vacancies agglomerating into vacancy clusters. Further annealing of the sample above 500 °C leads to recovery of dislocations.

High entropy alloys exhibit various combinations of interesting physical properties due to the formation of solid solution stabilized by high configurational entropy. High entropy alloy HfNbTaTiZr exhibits single phase solid solution with BCC structure when prepared by arc melting [1]. Grain refinement achieved in cold rolled samples after recrystallization remarkably enhanced ductility of this alloy [2]. Mechanical alloying by milling and subsequent sintering is a frequent production way of preparing fine grained alloys from chemical elements with high melting temperature. In addition, spark plasma sintering (SPS) method with applied pressure serves as a unique tool of powder metallurgy thanks to fast heating rates and low time of exposition to elevated temperatures. Therefore, the deformation energy introduced during mechanical alloying may be effectively consumed during short sintering process and presents the additional parameter for grain refinement. The present work presents characterization of HfNbTaTiZr alloy prepared by SPS.
Microstructure of samples prepared by SPS was compared with as cast ingots. The samples were characterized by X-ray diffraction and scanning electron microscopy. Positron annihilation spectroscopy was employed for characterization of defects introduced by SPS and their thermal stability.
[1] O.N. Senkov, J.M. Scott, S.V. Senkova. D.B. Miracle, C.F. Woodward: Journal of Alloys and Compounds 509, 6043-6048 (2011).
[2] O.N. Senkov, S.L. Semiatin; Journal of Alloys and Compounds 649, 1110-1123 (2015).

Understanding how the size, shape, and the aggregation state of the silver nanoparticles (NPs) are changed after integration into a target matrix is critical to enhance their performance, including molecular diagnostics, photonic and biomedical devices, which take advantage of the novel optical properties of these nanomaterials. In particular, the nanocomposites containing noble metal NPs dispersed in the polymer matrix by high-dose (> 1016 ions/cm2) implantation at low-energy ions (< 100 keV) can be used for the construction of plasmonic waveguides [1] and diffraction gratings [2]. Typically, form and size of Ag NPs in optically transparent matrices are connected with an appearance in visible absorption spectra of composite a surface plasmon resonance band. However, synthesis of Ag NPs by ion implantation in transparent polymer matrix such as polymethylmethacrylate (PMMA) has been found [1] to be quite difficult and unusual.
This problem can be solved with a powerful technique for the characterization of thin films – positron annihilation spectroscopy (PAS) using a variable-energy positron beam (VEPAS), – allowing depth-profiles from tens of nanometers up to several micrometers. This technique has been emerged as a key experimental tool for the understanding high-dose 40 keV boron-ion-implanted polymethylmethacrylate (B:PMMA) [3] with carbon nanostructures and Ag NPs loaded polymer brushes [4]. Also, the first attempt to find difference between the effects of carbonization and formation of Ag NPs in high-dose B:PMMA and Ag:PMMA nanocomposites has been done in the work [5] by using the Doppler broadening slow positron beam spectroscopy (DB-SPBS).
In the present work, the DB-SPBS technique was applied to characterize further the 30 keV Ag:PMMA nanocomposites fabricated by low-energy high-dose Ag-ion implantation. The results of depth profile of the S(Ep) parameter in the near-surface region of irradiated polymer were used to clarify indirectly a formation of Ag NPs in PMMA in dependence on ion dose. By comparative analysis with the S(Ep) parameter trend in polymer brushes with loaded Ag NPs [4], it is found that the density or mass of Ag NPs (‘Ag filling’) in Ag:PMMA increases as ion dose grows. The results obtained are discussed in terms of the positronium formation fraction in the irradiated part of polymer matrix and the model of carbon-shell Ag-core nanoparticles.
[1] A.L. Stepanov, Tech. Phys. 49, 143 (2004).
[2] M.F. Galyautdinov et al., Tech. Phys. Lett. 42, 182 (2016).
[3] T. Kavetskyy et al., J. Phys. Chem. B 118, 4194 (2014).
[4] G. Panzarasa et al., Nanotechnology 27, 02LT03 (2016).
[5] T. Kavetskyy et al., J. Phys.: Conf. Ser. 791, 012028 (2017).

A variety of advantageous thermal, electrical and mechanical properties of zirconium di-oxide (ZrO2, zirconia) make zirconia-based materials widely used in many industrial areas, in particular, in ceramic industry and other high-temperature applications. Doping of the ZrO2 host lattice by proper metal cations is a prerequisite of stabilisation of the high- temperature cubic and tetragonal phases down to room temperature as well as improvement of other functional properties. The use of nanopowders as initial substances in manufacturing ZrO2-based nanoceramics by sintering leads to well-homogenised materials of a low porosity. Due to an appreciable volume fraction of grain boundaries (GBs), pores and nanometer-sized open-volume defects associated to GBs become significant in nanopowders. Obviously, positron as well as positronium (Ps) atom becomes efficient
probes of microstructure evolution during production of ZrO2-based functional nanomaterials by sintering.
In the present contribution, investigation of several zirconia-based nanopowders as well as ceramics, obtained by sintering these nanopowders, will be reported. Nanopowders under study were doped with metal cations of various valency (Mg2+, Y3+, Cr3+, Ce4+) and differed also in thermal treatment. Doppler broadening (DB) measurements using slow-positron beam were conducted in the positron energy E ranging from 0.03 eV to 35 keV and the ordinary S and W shape parameters as well as the relative 3γ fractions were evaluated as functions of E. In Figure, an example of measured S(E) curves is given illustrating the sintering induced disappearance of open volume defects and para-Ps formation as well as grain growth could be observed. The VEPFIT models were fitted to the measured S(E), W(E) curves. The DB experiments were supplemented with the conventional positron lifetime, X-ray diffraction (XRD) and mass-density (MD) measurements. Nature and depth distributions of open-volume defects will be discussed on the basis of the slowpositron beam results correlated with the data on positron lifetimes, XRD and MD.

Palladium is well known for its excellent hydrogen absorption kinetics. The gravimetric hydrogen absorption capacity of Pd is however only 0.93 wt. %. Magnesium exhibits a high hydrogen absorption capacity up to 7.6 wt. %, however the hydrogen absorption kinetics is slow. The aim of this work was to create thin Pd-Mg multilayered films combining positive hydrogen absorption properties of both elements. Pd-Mg multilayers were deposited by RF magnetron sputtering on fused silica substrates coated with 100 nm thick Pd wetting layer. The multilayers consist of alternating Pd and Mg layers (3, 12 and 60) of the same thickness. Three types of Pd-Mg multilayers were compared: (i) as deposited samples, (ii) hydrogen gas loaded samples at room temperature and H2 pressure of 4000 Pa for 2 h, (iii) samples annealed up to 450°C under Ar atmosphere. Defect structure of Pd-Mg multilayers was characterized using variable energy positron annihilation spectroscopy. Doppler broadening of the annihilation photopeak was analyzed using the S and W line-shape parameters and the measured S(E) curves were fitted using the VEPFIT code. The development of the structure during the annealing of the films was monitored by in-situ X-ray diffraction. Atomic force microscopy was employed for the study of the surface morphology. All films were characterized by nanocrystalline structure with a high density of grain boundaries with open-volume defects capable of positron trapping. The density of grain boundaries is determined by the mean grain size which increases with increasing thickness of a single phase layer. Hydrogen loading led to buckling of the film and introduced additional defects into the film. Annealing of the multilayers leads to diffusion of Mg atoms into the Pd layers and precipitates of Mg-Pd phase are formed.

Fe₆₀Al₄₀ alloys exhibit disorder dependent magnetic phase transitions (MPT), e.g., a ferromagnetic disordered A2-phase turns into a paramagnetic ordered B2-phase [1]. The ordered B2-phase, formed due to annealing up to 500°C in vacuum can be reversed to the disordered A2-phase via ion-irradiation [2]. It has been shown that the physical origin of MPT is related to the so-called anti-site disorder (ASD), i.e., variations in the number of Fe-Fe nearest neighbors due to disordering of the system [3]. However, variations of the lattice parameter, secondary phases, and changes in the concentration and size of open volume defects may play an important role as well. Here, an excimer UV ns-laser has been utilized to induced defects and examine the role of ASD and defects onto magnetic properties of Fe₆₀Al₄₀. Samples of 40 nm thick Fe₆₀Al₄₀ films with different initial order levels were exposed to a range of laser fluences: (i) Ne+ irradiated fully-disordered (A2- Fe₆₀Al₄₀), and (ii) vacuum annealed ordered alloys (B2- Fe₆₀Al₄₀) and (iii) as-grown semi-disordered (A2/B2- Fe₆₀Al₄₀). It is seen that for laser pulses of fluences below 100 mJ·cm^-2 cause subtle changes to the magnetization depending on the Fe₆₀Al₄₀ initial state, whereas for fluences above 150 mJ·cm-2, strong increase in ferromagnetism is observed for all Fe60Al40 initial states. The laser irradiated samples were probed with the Positron Annihilation Spectroscopy (PAS) to analyze for the existence of vacancies and/or phase separation. Although the low fluence region shows nearly no variation in vacancy defect concentration, a slight increase in the number of Al atoms around defect sites is found. For the high fluence regime, it is seen that a large variation in vacancy defects occurs, followed by pronounced phase separation. Structural analysis of the phase separated films shows strong migration of Al atoms leaving behind Fe-enriched regions, consistent with the PAS spectra.
[1] M. O. Liedke et al., J. Appl. Phys. 117, 163908 (2015)
[2] J. Fassbender, et. al., Phys. Rev. B 77, 174430 (2008)
[3] R. Bali, et al., Nano Lett. 14, 435 (2014)

Systematic magnetic, electronic, and electrical studies on the Cu0.04Zn0.96O/Ga0.01Zn0.99O cell structure grown on (001) sapphire by the pulsed laser deposition technique show that the Cu multivalent (CuM+) ions modulate magnetic and resistive states of the cells. The magnetic moment is found to be reduced by ∼30% during the high resistance state (HRS) to low resistance state (LRS) switching. X-ray photoelectron spectroscopy results reveals an increase of the Cu+/Cu2+ oxidation state ratio (which has been determined by the relative positions of the Fermi level and the Cu acceptor level) during the HRS to LRS transition. This decreases the effective spin-polarized Cu2+−Vö−Cu+ channels and thus the magnetic moment. A conduction mechanism involving the formation of conductive filaments from the coupling of the CuM+ ions and Vö has been suggested.

Symmetries and localization properties of defect modes of a one-dimensionsional bi-component magnonic superlattice are theoretically studied. The magnonic superlattice can be seen as a periodic array of nanostripes, where stripes with different width, termed as defect stripes, are periodically introduced. By controlling the geometry of the defect stripes, a transition from dispersive to practically

at spin-wave defect modes can be observed inside the magnonic band gaps. It is shown that the spin-wave profile of the defect modes can be either symmetric or asymmetric by depending on the geometry of the defect. Due to the localization peculiarities of the defect modes, a particular magnonic superlattice is proposed, wherein the excitation of either symmetric or antisymmetric at modes is enabled at the same time. Also, it is demonstrated that the relative frequency position of the asymmetric mode inside the band gap does not significantly change with the application of an external field, while the symmetric modes move to the edges of the frequency band gaps. The results are complemented by numerical simulations, where an excellent agreement is observed between both methods. The proposed theory allows exploring different ways to control the dynamic properties of the defect modes in metamaterial magnonic superlattices, which can be useful for applications on multifunctional microwave devices operating over a broad frequency range.

The severe side effects encountered with platinum-based anticancer agents has driven the pursuit of new metal-based chemotherapeutics. The best examples of these are ruthenium compounds which have shown a promising potential to circumvent these side effects on account of their broad antiproliferative profile and novel mechanistic of action against cancer cells. Our work aims at the development of substitutionally inert Ru(II)-tris(diimine) complexes as new anticancer agents. Here we present the anticancer action and cytotoxicity mechanism of a Ru(dppz)2(CppH) cells [3]. The reported findings represent a major advancement towards achieving a site-directed spatially and temporally controlled anti-cancer activity from such metallo cytotoxics.

References
[1] V. Pierroz, T. Joshi, A. Leonidova, C. Mari, J. Schur, I. Ott, L. Spiccia, S. Ferrari, G. Gasser J. Am. Chem. Soc. 134 (2012) 20376−20387.
[2] T. Joshi, V. Pierroz, S. Ferrari, G. Gasser ChemMedChem 9 (2014) 1419–1427.
[3] T. Joshi, V. Pierroz, C. Mari, L. Gemperle, S. Ferrari, G. Gasser Angew. Chem. Int. Ed. 53 (2014) 2960–2963.

Aminoglycosides are one of the most well-studied classes of naturally occurring antibacterial agents [1]. Their antibiotic activity derives from their selective binding to the bacterial ribosomal RNA A-site, which ultimately leads to disruption of protein synthesis. Unfortunately, despite exhibiting a promising antibacterial profile, the widespread use of aminoglycosides as antibiotics has been hampered by their adverse side effects and the emergence of bacterial resistance. Herein, we present the synthesis of a series of new neomycin B conjugates featuring a polyazamacrocycle, 1,4,7,10-tetraazacyclododecane (cyclen), appended to the D-ribose ring, together with an examination of their A-site binding properties, as well as those of the corresponding Zn(II) complexes (C1–C3 and Zn(II)-C1–Zn(II)-C3). Since the high affinity of aminoglycosides for RNA is associated with the formation of complementary electrostatic interactions between protonated amine groups on the aminoglycosides and the RNA, the tethered cyclen macrocycle, enhances affinity for the A-site RNA motif due to the introduction of additional ionisable amino groups [2,3]. Furthermore, in agreement with previous findings that Zn(II)-cyclen complexes form reasonably strong interactions with phosphate groups as well as the deprotonated imide groups of the nucleobases, uracil and thymine, complexation of Zn(II) by cyclen in the neomycin B conjugates serves to enhance the affinity further still by allowing the conjugates to form coordination bonds with the RNA target [2,3]. The conjugates are worthy of further investigation as potential new antibiotic agents.

References: [1] Y. Tor, ChemBioChem 2003, 4, 998. [2] B. Kong, T. Joshi, et al., J. Inorg. Biochem. 2016, 162, 334. [3] T. Joshi, et. al., Acc. Chem. Res. 2015, 48, 2366.

The photodecomposition mechanism of trans,trans,trans-[Pt(N3)2(OH)2(py)2] (1, py = pyridine), an anticancer prodrug candidate, was probed using complementary Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), transient electronic absorption and UV-Vis spectroscopy. Data fitting using Principal Component Analysis (PCA) and multi-curve resolution alternating least squares, suggests the formation of a trans-[Pt(N3)(py)2(OH/H2O)] intermediate and trans [Pt(py)2(OH/H2O)2] as the final product upon 420 nm irradiation of 1 in water. Rapid disappearance of the hydroxido ligand stretching vibration upon irradiation is correlated with a -10 cm-1 shift to the anti-symmetric azido vibration, suggesting a possible second intermediate. Experimental proof of subsequent dissociation of azido ligands from platinum is presented, where at least one hydroxyl radical is formed in the reduction of Pt(IV) to Pt(II). Additionally, the photoinduced reaction of 1 with the nucleotide 5’-guanosine monophosphate (5’-GMP) was comprehensively studied, and the identity of key photoproducts was assigned with the help of ATR FTIR spectroscopy, mass spectrometry and density functional theory calculations. The identification of marker bands for some of these photoproducts (e.g., trans-[Pt(N3)(py)2(5’-GMP)] and trans-[Pt(py)2(5’-GMP)2] will aid elucidation of the chemical and biological mechanism of anticancer action of 1. In general, these studies demonstrate the potential of vibrational spectroscopic techniques as promising tools for studying such metal complexes.

In most industrial products, granular materials are often required to flow under gravity in various kinds of silo shapes and usually through an outlet in the bottom. There are several interrelated parameters which affect the flow, such as internal friction, bulk and packing density, hopper geometry, and material type. Due to the low spatial resolution of electrical capacitance tomography or scanning speed limitation of standard X-ray CT systems, it is extremely challenging to measure the flow velocity and possible centrifugal effects of granular materials flow effectively. However, the ultrafast electron beam X-ray CT scanner (ROFEX) opens new avenues of granular flow investigation due to its very high temporal resolution. This paper aims to track particles movements and evaluate the local grain velocity during silo discharging process in the case of mass flow. The study has considered the use of the Seramis material, which can also serve as a type of tracer particles after impregnation, due to its porous nature. The presented image processing and analysis approach allows satisfyingly measuring individual particle velocities but also tracking their movements.

European demand for chromium has grown dramatically, leading to the need for a detailed understanding of recycling of steel sludges and separation methods. To simulate these processes, we will use the radiotracer technique. ⁵¹Cr (T_1/2 = 27.7 d) was choosen as a radionuclide. The isotope can be produced by the nuclear reaction ^natV(p,n)⁵¹Cr at a cyclotron. We used our recently installed cyclotron Cyclone^® 18/9 (IBA) for the irradiation of ^natV (99.75% ⁵¹V). The vanadium foil was put in an aluminium holder with a diameter of 10 mm and a depth of 100 µm. The target was covered by a 100 µm thick aluminium foil. The irradiation was done at a beam of 16 MeV protons and a current of 10 µA for 4 hours. For the separation of ⁵¹Cr we established a multistage treatment. After cooling for 20 hours, the vanadium foil was dissolved with 2 ml conc. nitric acid. After addition of 20 mg iron(III) chloride, the hydroxide was subjected to a threefold cycle of precipitation with ammonia and dissolution with nitric acid. Vanadium(V) is soluble under these conditions. The separation of the radionuclide ⁵¹Cr and iron(III) was performed by ion exchange chromatography with AG 1-X8 (BIORAD) in conc. HCl. The ⁵¹Cr solution was eluted on the resin and the resin was washed six times with 2 ml conc. hydrochloric acid to remove the iron(III). The combined ⁵¹Cr solutions were evaporated to dryness and the residue was dissolved in 0.01 M sulfuric acid. The detection of ⁵¹Cr was done by gamma-counting (320 keV; 9.91%). The radiochemical yield was 66% at a production rate of 0.575 MBq/µAh.

Recent phase 2 trials have shown that BRAF/MEK inhibitors and immune checkpoint inhibitors are active in patients with melanoma brain metastases (MBM), reporting intracranial disease control rates of 50-75%. Furthermore, retrospective analyses suggest that combining stereotactic radiosurgery with immune checkpoint inhibitors or BRAF/MEK inhibitors prolongs overall survival. These data stress the need for interand multidisciplinary cooperation that takes into account the individual prognostic factors in order to establish the best treatment for each patient. Although the management of MBM has dramatically improved, a substantial number of patients still progress and die from brain metastases. Therefore, there is an urgent need for prospective studies in patients with MBM that focus on treatment combinations and sequences, new treatment strategies, and biomarkers of treatment response.
Moreover, further research is needed to decipher brain-specific mechanisms of therapy resistance.

Invited keynote presentation for the 3rd BGR-Rohstoffkonferenz in Hannover.

HIM-TOF-SIMS at HZDR

Purpose/Objective:

Assessment of accuracy and robustness of treatment planning on dual-energy CT (DECT) in a multi-step validation and clinical implementation scheme (Fig.1,2).

Material/Methods:

To ensure reliable translation of DECT into routine clinical application, scan settings and stopping-power prediction methods were optimized and validated using 13 different animal tissues and an anthropomorphic ground-truth phantom. The clinical relevance of DECT-based stopping-power prediction was evaluated on dual-spiral DECT scans of 102 brain-, 25 prostate- and 3 lung-tumor patients treated with protons. DECT-derived voxelwise correlations of CT number and stopping-power ratio (SPR) were used for adapting the clinically applied CT-number-to-SPR conversion (HLUT) and quantifying intra- and inter-patient variability.

Results:

The accuracy of DECT-based stopping-power prediction was within 0.3% stopping-power and 1mm range uncertainty of validation measurements. Clinically relevant mean range shifts (±1SD) of 1.2(±0.7)% for brain-, 1.7(±0.5)% for prostate- and 2.2(±1.2)% for lung-tumor patients were obtained between dose calculations using HLUT or DECT-derived SPR. These deviations were significantly reduced (p<<0.001, two-sample t-test) below 0.3% by HLUT refinement based on patient-specific DECT information. Still, the remaining large intra-patient soft tissue diversity of approx. 6% (95% CI) and age-dependent inter-patient bone variability of 5% cannot be considered by any HLUT-based range prediction.

Conclusion:

Additional tissue information provided by DECT allows for accurate stopping-power prediction and incorporation of patients’ tissue diversity in treatment planning. These advantages can contribute to reduce CT-related range uncertainty and have been gradually translated in our clinical routine: (1) DECT-derived pseudo-monoenergetic CT dataset with generic HLUT, (2) DECT-based HLUT adaptation and soon (3) patient-specific DECT-basted stopping-power prediction.

We report on tailoring ionization-induced injection in laser wakefield acceleration so that the electron injection process is self-truncating following the evolution of the plasma bubble. Robust generation of high-quality electron beams with shot-to-shot fluctuations of the beam parameters better than 10% is presented in detail. As a novelty, the scheme was found to enable well-controlled yet simple tuning of the injected charge while preserving acceleration conditions and beam quality. Quasimonoenergetic electron beams at several 100MeV energy and 15% relative energy spread were routinely demonstrated with a total charge of the monoenergetic feature reaching 0.5 nC. Finally these unique beam parameters, suggesting unprecedented peak currents of several 10 kA, are systematically related to published data on alternative injection schemes.

A total of 230.000 tons of the so called “Theisenschlamm”, a waste material of the former copper shale processing in the Mansfeld region, was deposited between the years 1978 and 1990. Besides about 20 wt.-% of zinc and minor amounts of lead, copper and tin, this material also contains valuable strategic elements, like rhenium and germanium. Nowadays rhenium is used as an important alloying element in nickel-base superalloys, or in catalysts.
The r⁴-project “Theisenschlamm” aims at a recovery of the valuable metal content by bioleaching, followed by element specific separation methods. An effective method for the selective separation and concentration of metals is solvent extraction where an organic phase is used to extract the elements of interest from an aqueous phase. But since the metal concentrations in the bioleaching solution are low, the processing is challenging. However, there are multiple parameters allowing an optimization of the solvent extraction process. The findings for a selective enrichment of rhenium from synthetic (bioleaching) solution will be presented in this talk.

The r⁴-project "Theisenschlamm" focuses on the recovery of elements of strategic economic importance (like Rhenium or Molybdenum). The first step within the research approach is bioleaching of the Theisenschlamm, which is a waste material of the former copper shale processing in the Mansfeld region (Germany). As a next process step the project partners investigate different element selective separation methods to recover the valuable elements from the bioleaching solution. An efficient rhenium recovery from synthetic (bioleaching) solutions is achieved using solvent extraction with teriary amines. It could be shown that rhenium can be enriched in the organic phase and that a good selectivity over zinc, copper, cobalt, germanium and iron(III) is obtained.

The exact nature of the radiation defects causing hardening in reactor structural steels consists of several components that are not yet clearly determined. While generally, the hardening is attributed to dislocation loops, voids and secondary phases (radiation-induced precipitates), recent advanced experimental and computational studies point to the importance of solute-rich clusters (SRCs). Depending on the exact composition of the steel, SRCs may contain Mn, Ni and Cu (e.g. in reactor pressure vessel steels) or Ni, Cr, Si, Mn (e.g. in high-chromium steels for generation IV and fusion applications). One of the hypotheses currently implied to explain their formation is the process of radiation-induced diffusion and segregation of these elements to small dislocation loops (heterogeneous nucleation), so that the distinction between SRCs and loops becomes somewhat blurred. In this work, we perform an atomistic study to investigate the enrichment of loops by Ni and Cr solutes and their interaction with an edge dislocation. The dislocation loops decorated with Ni and Cr solutes are obtained by Monte Carlo simulations, while the effect of solute segregation on the loop's strength and interaction mechanism is then addressed by large scale molecular dynamics simulations. The synergy of the Cr-Ni interaction and their competition to occupy positions in the dislocation loop core are specifically clarified.

Aspiration of low-pH gastric fluid leads to an initial pneumonitis, which may become complicated by subsequent pneumonia or acute respiratory distress syndrome. Current treatment is at best supportive, but there is growing experimental evidence on the significant contribution of both neutrophils and platelets in the development of this inflammatory pulmonary reaction, a condition that can be attenuated by several medicinal products. This review aims to summarize novel findings in experimental models on pathomechanisms after an acid-aspiration event. Given the clinical relevance, specific emphasis is put on deduced potential experimental therapeutic approaches, which make use of the characteristic alteration of microcirculation in the injured lung.