Imaging low-energy positron beams in real-time with unprecedented resolution.

Particle beams focused to micrometer-sized spots play a crucial role in forefront research using low-energy positrons. Their expedient and wide application, however, requires highly-resolved, fast beam diagnostics. We have developed two different methods to modify a commercial imaging sensor to make it sensitive to low-energy positrons. The first method consists in removing the micro-lens array and Bayer filter from the sensor surface and depositing a phosphor layer in their place. This procedure results in a detector capable of imaging positron beams with energies down to a few tens of eV, or an intensity as low as [Formula: see text] when the beam energy exceeds 10 [Formula: see text]. The second approach omits the phosphor deposition; with the resulting device we succeeded in detecting single positrons with energies upwards of [Formula: see text] and efficiency up to 93%. The achieved spatial resolution of 0.97 [Formula: see text] is unprecedented for real-time positron detectors.

Total-reflection high-energy positron diffractometer at NEPOMUC - Instrumentation, simulation, and first measurements.

We report the instrumentation of a new positron diffractometer that is connected to the high-intensity positron beam at the neutron induced positron source Munich. Crucial elements for the adaption of the positron beam are presented, which include the magnetic field termination, the optional transmission-type remoderator for brightness enhancement, and the electrostatic system for acceleration and beam optics. The positron trajectories of the remoderated and the twofold remoderated beam have been simulated to optimize the system, i.e., to obtain a coherent beam of small diameter. Within a first beamtime, we tuned the system and characterized the direct beam. For the twofold remoderated beam of 10 keV energy, we experimentally observe a beam diameter of d < 1.3 mm, which agrees well with the simulation.

Morphology of Thin Film Composite Membranes Explored by Small-Angle Neutron Scattering and Positron-Annihilation Lifetime Spectroscopy.

The morphology of thin film composite (TFC) membranes used in reverse osmosis (RO) and nanofiltration (NF) water treatment was explored with small-angle neutron scattering (SANS) and positron-annihilation lifetime spectroscopy (PALS). The combination of both methods allowed the characterization of the bulk porous structure from a few Å to µm in radius. PALS shows pores of 4.5 Å average radius in a surface layer of about 4 m thickness, which become 40% smaller at the free surface of the membranes. This observation may correlate with the glass state of the involved polymer. Pores of similar size appear in SANS as closely packed pores of 6 Å radius distributed with an average distance of 30 Å. The main effort of SANS was the characterization of the morphology of the porous polysulfone support layer as well as the fibers of the nonwoven fabric layer. Contrast variation using the media H2O/D2O and supercritical CO2 and CD4 identified the polymers of the support layers as well as internal heterogeneities.

Crosslinked PVA/SSA proton exchange membranes: correlation between physiochemical properties and free volume determined by positron annihilation spectroscopy.

Two processes for crosslinking polyvinyl alcohol (PVA) with sulfosuccinic acid (SSA) and thermal crosslinking were used to fabricate a proton exchange membrane (PEM). Such PEMs are used in different fields involving fuel cell applications. The crosslinking reaction between PVA and SSA was confirmed using Fourier-transform infrared (FTIR) spectroscopy. The characterization of the prepared membranes, namely, ion exchange capacity (IEC), thermal analyses, water uptake, and ionic conductivity, was carried out. The IEC of the prepared membranes was found to be between 0.084 and 2.086 mmol g-1, resulting in an essential increase in the ionic conductivity. It was observed that the ionic conductivity was in the range of 0.003-0.023 S cm-1, depending on both temperature and SSA content. From the thermogravimetric analysis (TGA) results, it was revealed that the thermal stability of the crosslinked membranes improved. Moreover, water uptake decreased with increasing SSA content. Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of the PVA/SSA membranes and their distribution at different ambient temperatures and relative humidity (RH) values. At room temperature, no significant change was observed in the free-volume holes up to 15 wt% SSA; thereafter, the size of the free-volume holes increased with the SSA content. The PALS results show that at different humidity values, the size of the free-volume holes for crosslinked PVA/SSA membranes is lower than those for Nafion membranes, i.e., the gas permeability for the prepared PVA/SSA membranes is less than that for the Nafion membrane. In addition, a strong correlation between the water uptake, ionic conductivity, tensile strength, and free-volume holes was observed.

Nature of the Positron State in CdSe Quantum Dots.

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor quantum dots (QDs) embedded in thin films. The nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab initio calculations of the positron wave function and lifetime employing a recent formulation of the weighted density approximation demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the long-standing question regarding the nature of the positron state in semiconductor QDs and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques.

Anomalous molecular infiltration in graphene laminates.

Graphene laminated (GL) coatings formed by stacked few layer graphene (FLG) nanocrystals were deposited on low-density polyethylene (PE) films by the mechanical rubbing technique. Molecular transport through the bilayer membrane was studied by the gas phase permeation technique by monitoring the CO2, N2 and 2H2 transport fluxes in transient conditions. The results evidenced that the transport exhibited anomalous character. The experimental data could be reproduced assuming that the penetrant concentration in the GL coating, cint(t), reached a saturation value cs following compressed exponential kinetics cint(t) = cs[1 - e-(λrelt)ß]. The relaxation time τrel = 1/λrel showed thermally activated behavior, and its value increased with the kinetic diameter of the penetrant molecules. The critical exponent ß = 1.5 ± 0.1 for CO2 and N2 and ß = 2.0 ± 0.1 for 2H2 did not change with temperature. Positron annihilation lifetime spectroscopy (PALS) analysis indicated that the average cross-section (hg) of the cavities in the GL coating exhibited comparable size to the kinetic diameter (σk) of the penetrant molecules. The results could be explained by assuming that the molecular infiltration in the GL structure occurred in nano-channels having distributed path lengths where the penetrant transport obeyed a configurational diffusion mechanism.

Structural Insights into Water-Based Spider Silk Protein-Nanoclay Composites with Excellent Gas and Water Vapor Barrier Properties.

Nature reveals a great variety of inorganic-organic composite materials exhibiting good mechanical properties, high thermal and chemical stability, and good barrier properties. One class of natural bio-nanocomposites, e.g. found in mussel shells, comprises protein matrices with layered inorganic fillers. Inspired by such natural bio-nanocomposites, the cationic recombinant spider silk protein eADF4(κ16) was processed together with the synthetic layered silicate sodium hectorite in an all-aqueous setup. Drop-casting of this bio-nanocomposite resulted in a thermally and chemically stable film reflecting a one-dimensional crystal. Surprisingly, this bio-nanocomposite coating was, though produced in an all-aqueous process, completely water insoluble. Analyzing the structural details showed a low inner free volume due to the well-oriented self-assembly/alignment of the spider silk proteins on the nanoclay surface, yielding high oxygen and water vapor barrier properties. The here demonstrated properties in combination with good biocompatibility qualify this new bio-nanocomposite to be used in packaging applications.

Positron spectroscopy of point defects in the skyrmion-lattice compound MnSi.

Outstanding crystalline perfection is a key requirement for the formation of new forms of electronic order in a vast number of widely different materials. Whereas excellent sample quality represents a standard claim in the literature, there are, quite generally, no reliable microscopic probes to establish the nature and concentration of lattice defects such as voids, dislocations and different species of point defects on the level relevant to the length and energy scales inherent to these new forms of order. Here we report an experimental study of the archetypical skyrmion-lattice compound MnSi, where we relate the characteristic types of point defects and their concentration to the magnetic properties by combining different types of positron spectroscopy with ab-initio calculations and bulk measurements. We find that Mn antisite disorder broadens the magnetic phase transitions and lowers their critical temperatures, whereas the skyrmion lattice phase forms for all samples studied underlining the robustness of this topologically non-trivial state. Taken together, this demonstrates the unprecedented sensitivity of positron spectroscopy in studies of new forms of electronic order.

Novel pulsed particle accelerator for energy dependent positron re-emission experiments.

We report on a novel device for particle acceleration based on elevation of the potential energy of beam pulses. This so-called energy elevator is particularly beneficial if both the particle source and the sample have to be near ground potential due to experimental constraints. We applied this new technique to enable depth dependent measurements of re-emitted positrons using the surface spectrometer at the NEPOMUC positron beam facility. First, a two-stage bunching system is used to generate positron pulses with a repetition rate of 5 MHz and a duration of 1.663(5) ns before their energy is raised to several keV. The whole system was shown to work with an exceptional efficiency of 88%. We demonstrated the usability of our setup by investigating the positron re-emission spectra of Ni and Pd as function of positron implantation energy. For Ni the positron work function could be determined to be ΦNi (+)=-1.4(2)eV. In addition, as predicted by theory, our experimental findings imply a positive positron work function for Pd.

Local electron-electron interaction strength in ferromagnetic nickel determined by spin-polarized positron annihilation.

We employ a positron annihilation technique, the spin-polarized two-dimensional angular correlation of annihilation radiation (2D-ACAR), to measure the spin-difference spectra of ferromagnetic nickel. The experimental data are compared with the theoretical results obtained within a combination of the local spin density approximation (LSDA) and the many-body dynamical mean-field theory (DMFT). We find that the self-energy defining the electronic correlations in Ni leads to anisotropic contributions to the momentum distribution. By direct comparison of the theoretical and experimental results we determine the strength of the local electronic interaction U in ferromagnetic Ni as 2.0 ± 0.1 eV.

Spin-Resolved Fermi Surface of the Localized Ferromagnetic Heusler Compound Cu2MnAl Measured with Spin-Polarized Positron Annihilation.

We determined the bulk electronic structure of the prototypical Heusler compound Cu(2)MnAl by measuring the angular correlation of annihilation radiation using spin-polarized positrons. To this end, a new algorithm for reconstructing 3D densities from projections is introduced that allows us to corroborate the excellent agreement between our electronic structure calculations and the experimental data. The contribution of each individual Fermi surface sheet to the magnetization was identified, and summed to a total spin magnetic moment of 3.6±0.5 µ(B)/f.u..

The free volume in dried and H2O-loaded biopolymers studied by positron lifetime measurements.

We present experiments on glucose-gelatin compounds using positron annihilation lifetime spectroscopy (PALS) in order to study the behavior of the free volume dependent on H2O loading, drying, and uniaxial pressure. A semiempirical quantum mechanical model was applied in order to correlate the lifetime of orthopositronium in nanoscaled voids to the void size. This allowed us to determine the absolute value of the mean void radius in the biopolymer samples. In addition, the variation of the total free volume of the differently treated samples is quantified and illustrated by a log-normal distribution function. Most interesting results have been obtained after saturation loading with H2O that leads to the formation of voids with a mean size of 84.3(1.9) Å(3) and to an increase of the total free volume by a factor of 2.5. This observation in the swelled sample is explained by the entropy elastic regime well above the glass transition temperature that greatly facilitates the formation of free volume. Differential scanning calorimetry (DSC) measurements were performed in order to determine the glass transition temperature and to support the interpretation of the results obtained by PALS.

The source-sample stage of the new two-dimensional angular correlation of annihilation radiation spectrometer at Technische Universität München.

Angular correlation of annihilation radiation (ACAR) is a well established technique for the investigation of the electronic structure. A major limitation of ACAR studies is the available positron flux at a small spot on the sample. For this reason, the focus of this work is put on the discussion of a newly developed source-sample stage of the new 2D-ACAR spectrometer at Technische Universität München which uses an optimized static magnetic field configuration to guide the positrons onto the sample. The achieved spot diameter is d(FWHM) = 5.4 mm, with a high efficiency over the whole energy spectrum of the (22)Na positron source. The implications of the performance of the source-sample stage are discussed with regard to 2D-ACAR measurements of single crystalline α-quartz, which serves as a model system for the determination of the total resolution. A value of (1.53 × 1.64) mrad(2) FWHM was achieved at room temperature.

Free volumes in bulk nanocrystalline metals studied by the complementary techniques of positron annihilation and dilatometry.

Free-volume type defects, such as vacancies, vacancy-agglomerates, dislocations, and grain boundaries represent a key parameter in the properties of ultrafine-grained and nanocrystalline materials. Such free-volume type defects are introduced in high excess concentration during the processes of structural refinement by severe plastic deformation. The direct method of time-differential dilatometry is applied in the present work to determine the total amount and the kinetics of free volume by measuring the irreversible length change upon annealing of bulk nanocrystalline metals (Fe, Cu, Ni) prepared by high-pressure torsion (HPT). In the case of HPT-deformed Ni and Cu, distinct substages of the length change upon linear heating occur due to the loss of grain boundaries in the wake of crystallite growth. The data on dilatometric length change can be directly related to the fast annealing of free-volume type defects studied by in situ Doppler broadening measurements performed at the high-intensity positron beam of the FRM II (Garching, Munich, Germany).

In situ probing of fast defect annealing in Cu and Ni with a high-intensity positron beam.

A high-intensity positron beam is used for specific in situ monitoring of thermally activated fast defect annealing in Cu and Ni on a time scale of minutes. The atomistic technique of positron-electron annihilation is combined with macroscopic high-precision length-change measurements under the same thermal conditions. The combination of these two methods as demonstrated in this case study allows for a detailed analysis of multistage defect annealing in solids distinguishing vacancies, dislocations, and grain growth.

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects.

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.