Beamline P04 Research Articles

Natural-linewidth measurements of the 3C and 3D soft-x-ray transitions in Ni xix

We used the monochromatic soft-x-ray beamline P04 at the synchrotron-radiation facility PETRA III to resonantly excite the strongest 2p−3d transitions in neonlike Ni ions, [2p6]J=0→[(2p5)1/23d3/2]J=1 and [2p6]J=0→[(2p5)3/23d5/2]J=1, respectively dubbed 3C and 3D, achieving a resolving power of 15 000 and signal-to-background ratio of 30. We obtain their natural linewidths, with an accuracy of better than 10%, as well as the oscillator-strength ratio f(3C)/f(3D)=2.51(11) from analysis of the resonant fluorescence spectra. These results agree with those of previous experiments, earlier predictions, and our own advanced calculations. Published by the American Physical Society 2024

In Situ Synchrotron Investigations of Beam Diameter Influence on Vapor Capillary Formation during Laser Beam Welding of Copper Alloy with a Blue Laser Beam Source

Laser beam welding as a reliable tool for high-precision joining of batteries or microelectronics is more and more the choice for achieving reproducible results in production processes. In addition to a high automation capability, the precise control of the energy deposition into the material plays an important role, especially when highly reflective materials, such as copper or aluminum, must be welded together. Alongside the use of highly brilliant fiber lasers in the near-infrared range with a focal diameter of a few tens of micrometers, diode lasers in the wavelength range of 445 nm are increasingly being used. Here, beam diameters of a few hundred micrometers can be achieved. With a wavelength of 445 nm, the absorptivity in copper can be increased by more than a factor of 10 compared to a near-infrared laser beam sources in solid state at room temperature. This paper presents the in situ X-ray observation of laser welding processes on CuSn6 with a laser beam source with a wavelength of 445 nm using synchrotron radiation at DESY Petra III Beamline P07 EH4 in Hamburg, Germany. For the experiments, the laser radiation was focused via two separate optics to focal diameters of 362 µm and 609 µm. To characterize the dynamics of the vapor capillaries depending on the different focal diameters dF, the parameters were varied with respect to laser power PL and feed rate v. For the investigations, a synchrotron beam of 2 × 2 mm2 in size with a photon energy of 89 keV was used, and the material samples were analyzed by means of phase-contrast videography to show the boundaries between solid, liquid, and gaseous material phases. The results of this paper show the welding depths achieved and how the geometry of the vapor capillary behaves by changing the focal diameter, laser power and feed rate.

In-situ observation of end crater crack mechanisms in AA7075 during laser beam welding using synchrotron radiation

AA7075 is increasingly used in the aerospace industry due to its excellent strength to weight ratio. However, due to an extended solidification interval of its alloy components magnesium, zinc and copper, it is highly susceptible to solidification cracking and thus has limited suitability for laser beam welding processing. The formation of end crater cracks is a particular challenge. This study investigates the formation and propagation of cracks in AA7075 during laser beam welding at different beam diameters, feed rates and laser powers by using an in-situ X-ray high-speed imaging technique utilizing synchrotron radiation. The experiments were conducted at the German Electron-Synchrotron (DESY) at Petra III, beamline P07. The results show a correlation between cumulative crack length, solidification rate and energy input, providing important insights to improve the weldability of AA7075.

How reduction temperature influences the structure of perovskite-oxide catalysts during the dry reforming of methane.

Dry reforming of methane is a promising reaction to convert CO2 and combat climate change. However, the reaction is still not feasible in large-scale industrial applications. The thermodynamic need for high temperatures and the potential of carbon deposition leads to high requirements for potential catalyst materials. As shown in previous publications, the Ni-doped perovskite-oxide Nd0.6Ca0.4Fe0.97Ni0.03O3 is a potential candidate as it can exsolve highly active Ni nanoparticles on its surface. This study focused on controlling the particle size by varying the reduction temperature. We found the optimal temperature that allows the Ni nanoparticles to exsolve while not yet enabling the formation of deactivating CaCO3. Furthermore, the exsolution process and the behaviour of the phases during the dry reforming of methane were investigated using in situ XRD measurements at the DESY beamline P02.1 at PETRA III in Hamburg. They revealed that the formed deactivated phases would, at high temperatures, form a brownmillerite phase, thus hinting at a potential self-healing mechanism of these materials.

Developments on the powder diffraction and total scattering beamline P02.1, PETRA III, DESY

Developments on the powder diffraction and total scattering beamline P02.1, PETRA III, DESY

High-energy interference-free K-lines synchrotron X-ray fluorescence microscopy of rare earth elements in hyperaccumulator plants.

Synchrotron-based micro-X-ray fluorescence analysis (µXRF) is a non-destructive and highly sensitive technique. However, element mapping of rare earth elements (REEs) under standard conditions requires care, since energy-dispersive detectors are not able to differentiate accurately between REEs L-shell X-ray emission lines overlapping with K-shell X-ray emission lines of common transition elements of high concentrations. We aim to test REE element mapping with high-energy interference-free excitation of the REE K-lines on hyperaccumulator plant tissues and compare with measurements with REE L-shell excitation at the microprobe experiment of beamline P06 (PETRA III, DESY). A combination of compound refractive lens optics (CRLs) was used to obtain a micrometre sized focussed incident beam with an energy of 44 keV and an extra-thick silicon drift detector (SDD) optimised for high-energy X-ray detection to detect the K-lines of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr) and neodymium (Nd) without any interferences due to line overlaps. High-energy excitation from La to Nd in the hyperaccumulator organs was successful but compared to L-line excitation less efficient and therefore slow (∼10-fold slower than similar maps at lower incident energy) due to lower flux and detection efficiency. However, REE K-lines do not suffer significantly from self-absorption, which makes XRF-tomography of millimetre-sized frozen-hydrated plant samples possible. The K-line excitation of REEs at the P06 CRL setup has scope for application in samples that are particularly prone to REE interfering elements, such as soil samples with high concomitant Ti, Cr, Fe, Mn, Ni concentrations.

Soft X-Ray-induced Dimerization of Methane

Carbon 1s excitation of methane, CH4, has been studied in the gas phase using the ion trap integrated with the photon–ion instrument at PETRA III/DESY and soft X-rays from the beamline P04. The created photoions are stored within the ion trap so that in further steps the photoions can undergo reactions with neutral methane molecules. The ionic photoproducts as well as reaction products created thereby are mass-over-charge analyzed by an ion time-of-flight spectrometer. Besides the photoions, product ions with up to three carbon atoms are found. In contrast to experiments using vacuum ultraviolet radiation, especially highly reactive product ions with a small number of hydrogen atoms such as and are found, which are important precursors for larger hydrocarbons such as C6H6. Possible production routes of the product ions are analyzed on the basis of a model that considers the probabilities for photofragmentation and the first subsequent chemical reaction step. The model indicates that the high degree of fragmentation by photons with energies around 280 eV is favoring these products. The results of the measurements show that the products like and can be generated by a single collision of the ionization product with neutral methane. The results suggest that soft X-rays might be important for chemical reactions in planetary atmospheres, which has usually not been taken into account. However, due to the high degree of fragmentation and large cross sections involved, they can have a large influence even when the corresponding photon flux is rather small.

An integrated ion trap for the photon-ion spectrometer at PETRA III.

We have added a multipole ion trap to the existing photon-ion spectrometer at PETRA III (PIPE). Its hybrid structure combines a ring-electrode trap with a segmented 16-pole trap. The interaction of gases and ions with extreme ultraviolet radiation from the beamline P04 is planned to be investigated with the newly installed multipole trap. The research focus lies on radiation-induced chemical reactions that take place in the interstellar medium or in the atmospheres of planets, including natural as well as man-made processes that are important in the Earth's atmosphere. In order to determine the mass-to-charge ratio of the stored ions as efficiently as possible, we are using an ion time-of-flight spectrometer. With this technique, all stored ions can be detected simultaneously. To demonstrate the possibilities of the trap setup, two experiments have been carried out: The photoionization of xenon and the ion-impact ionization of norbornadiene. This type of ion-impact ionization can, in principle, also take place in planetary atmospheres. In addition to ionization by photon or ion impact, chemical reactions of the trapped ions with neutral atoms or molecules in the gas phase have been observed. The operation of the trap enables us to simulate conditions similar to those in the ionosphere.

Trace-element analysis of mineral grains in Ryugu rock fragment sections by synchrotron-based confocal X-ray fluorescence

A fundamental parameter-based quantification scheme for confocal XRF was applied to sub-micron synchrotron radiation X-ray fluorescence (SR-XRF) data obtained at the beamline P06 of the Deutsches Elektronen-Synchrotron (DESY, Hamburg, Germany) from two sections C0033-01 and C0033-04 that were wet cut from rock fragment C0033 collected from Cb-type asteroid (162173) Ryugu by JAXA’s Hayabusa2 mission. Trace-element quantifications show that C0033 bulk matrix is CI-like, whereas individual mineral grains (i.e., magnetite, pyrrhotite, dolomite, apatite and breunnerite) show, depending on the respective phase, minor to strong deviations. The non-destructive nature of SR-XRF coupled with a new PyMca (a Python toolkit for XRF data analysis)-based quantification approach, performed in parallel with the synchrotron experiments, proves to be an attractive tool for the initial analysis of samples from return missions, such as Hayabusa2 and OSIRIS-REx, the latter returning material from a B-type asteroid (101955) Bennu in 2023.Graphical

In-situ analysis of the elastic-plastic characteristics of high strength dual-phase steel

Modeling the elastic behavior of dual-phase steels is complex due to the strain dependency of Young's modulus and high elastic nonlinearity. Since it is assumed that reasons for this are to be found in microstructural behavior, microscopic in-situ analysis are necessary, but due to the overlap of the martensite and ferrite peaks, the evaluation of diffraction profiles is highly complex. Within this work, CR590Y980T (DP1000) is investigated in a continuous cyclic tensile and tension-compression test under synchrotron radiation at High Energy Material Science beamline P07 in Petra III, DESY. On basis of additional EBSD measurements, an evaluation approach is shown to analyze the dual-phase diffraction profiles in such a way that martensite and ferrite can be separated for three lattice planes. The origin of the specific elastic-plastic behavior of dual-phase steels in terms of onset of yielding, anelasticity or early re-yielding is analyzed on the basis of lattice strains and interphase stresses. For this, the time-synchronously measured micro data is correlated with the macro stress-strain relationship and thermoelastic effect. The results help to better understand strain-dependent elastic-plastic behavior of DP steels on a micro level and provide great potential to improve characterization and modeling in terms of springback prediction.

The powder diffraction and total scattering beamline P02.1 at PETRA III, DESY

The powder diffraction and total scattering beamline P02.1 at PETRA III, DESY

In-situ analysis of the thermoelastic effect and its relation to the onset of yielding of low carbon steel

The thermoelastic effect indicates the dependency of temperature and volume change in the material and, due to the heat released during plastic deformation, a temperature minimum occurs in the region of the onset of yielding. An experimental setup is presented for the microscopic analysis of the thermoelastic effect, which allows high precision measurements of specimen. In-situ diffraction experiments were performed for a single phase low carbon steel HC260Y using synchrotron diffraction at the High Energy Material Science beamline P07 in Petra III, DESY. This allows a direct comparison of the onset of yielding by observing the evolution of lattice strains and dislocations densities with the specimen temperature in a continuous cyclic test having high measuring frequency and accuracy. Therefore, the lattice strains are evaluated based on the peak shift of several lattice planes and the dislocation density is estimated based on the micro strain due to peak broadening. The results prove existing assumptions about the relation between the thermoelastic effect and the onset of yielding and clearly qualify the temperature-based determination method for material characterization on a microstructural basis. The usefulness of the temperature elasticity parameters is shown exemplarily with the determination of loading moduli and compared to existing methods.

Simultaneous imaging and diffraction in the dynamic diamond anvil cell.

The ability to visualize a sample undergoing a pressure-induced phase transition allows for the determination of kinetic parameters, such as the nucleation and growth rates of the high-pressure phase. For samples that are opaque to visible light (such as metallic systems), it is necessary to rely on x-ray imaging methods for sample visualization. Here, we present an experimental platform developed at beamline P02.2 at the PETRA III synchrotron radiation source, which is capable of performing simultaneous x-ray imaging and diffraction of samples that are dynamically compressed in piezo-driven diamond anvil cells. This setup utilizes a partially coherent monochromatic x-ray beam to perform lensless phase contrast imaging, which can be carried out using either a parallel- or focused-beam configuration. The capabilities of this platform are illustrated by experiments on dynamically compressed Ga and Ar. Melting and solidification were identified based on the observation of solid/liquid phase boundaries in the x-ray images and corresponding changes in the x-ray diffraction patterns collected during the transition, with significant edge enhancement observed in the x-ray images collected using the focused-beam. These results highlight the suitability of this technique for a variety of purposes, including melt curve determination.

Determination of the through-plane profile of vanadium species in hydrated Nafion studied with micro X-ray absorption near-edge structure spectroscopy - proof of concept.

Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2+. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2+ inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.

Role of L -shell single and double core-hole production and decay in m -fold ( 1≤m≤6 ) photoionization of the Ar+ ion

Multiple ionization of the ${\mathrm{Ar}}^{+}(3{s}^{2}3{p}^{5})$ ion by a single photon has been investigated in the photon-energy range 250--1800 eV employing the photon-ion merged-beams technique. Absolute partial cross sections were measured for all ${\mathrm{Ar}}^{(1+m)+}$ product-ion channels with $1\ensuremath{\le}m\ensuremath{\le}6$ covering a size range from several tens of Mb down to a few b. Narrow $2p$-subshell excitation resonances were observed in all channels up to quadruple ionization at a photon-energy bandwidth of 52 meV. Double excitations involving a $2p$ and a $3s$ or $3p$ electron were also studied at high resolution and the measurements of the broad $2s$ excitation resonances directly showed their natural widths. Contributions of direct photo double ionization (PDI) to the production of the highest final Ar ion charge states are revealed, with PDI of the $2s$ subshell being mainly responsible for the production of ${\mathrm{Ar}}^{7+}$. The experiment made use of the PIPE setup installed at beamline P04 of the PETRA III synchrotron light source of DESY in Hamburg. The measurements were supported by theoretical calculations to identify the main contributions to the observed cross sections. Comparisons of theory and experiment show remarkable agreement but also hint to additional ionization mechanisms that are not considered in the theoretical models such as core ionization accompanied by excitations with subsequent Auger decays leading to net $m$-fold ionization with $m\ensuremath{\ge}4$.

Investigation of the Effects of Low‐Pressure Carburizing Process Parameters on Microstructural Evolution by Means of In Situ Synchrotron X‐Ray Diffraction

In situ X‐ray diffraction experiments during low‐pressure carburizing processes are performed at the German Electron Synchrotron Facility, Beamline P07, in Hamburg, Germany, with a specially developed process chamber. Microstructural evolution is precisely analyzed based on diffraction data, and several process parameters are varied. The investigations focus on boost and diffusion steps in which carbon donor gas interacts with the hot steel surface and carbon atoms diffuse through the sample. An increased process temperature leads to higher carbon absorption during the boost step, especially at the early stages of the process. Regardless of process parameters, austenite saturation is reached in a few seconds. Therefore, longer boost step duration and/or a higher acetylene amount does not directly increase the carbon profile; instead, this would only increase the amount of carbides formed on the surface, which would contribute to the carbon profile by dissolution in the following steps. Therefore, shorter and a high number of boost steps are recommended for high efficiency. The cementite formation rate shows a similar trend with austenite saturation. It is very fast at the beginning and then stays almost constant. Therefore, introducing acetylene to the furnace after that point has no positive effect on the carburization.

Planar refractive lenses made of SiC for high intensity nanofocusing.

We report on the manufacturing and testing of the first nanofocusing refractive lenses made of single-crystal silicon carbide. We introduce the fabrication process based on lithography, followed by deep isotropic etching. The lenses were characterized at the energy of 12 keV at the beamline P06 of the synchrotron radiation source PETRA III. A focal spot of 186 nm×275 nm has been achieved with a lens working distance of 29 mm.

Multi-analyser detector (MAD) for high-resolution and high-energy powder X-ray diffraction.

For high-resolution powder diffraction in material science, high photon energies are necessary, especially for in situ and in operando experiments. For this purpose, a multi-analyser detector (MAD) was developed for the high-energy beamline P02.1 at PETRA III of the Deutsches Elektronen-Synchrotron (DESY). In order to be able to adjust the detector for the high photon energies of 60 keV, an individually adjustable analyser-crystal setup was designed. The adjustment is performed via piezo stepper motors for each of the ten channels. The detector shows a low and flat background as well as a high signal-to-noise ratio. A range of standard materials were measured for characterizing the performance. Two exemplary experiments were performed to demonstrate the potential for sophisticated structural analysis with the MAD: (i) the structure of a complex material based on strontium niobate titanate and strontium niobate zirconate was determined and (ii) an in situ stroboscopy experiment with an applied electric field on a highly absorbing piezoceramic was performed. These experiments demonstrate the capabilities of the new MAD, which advances the frontiers of the structural characterization of materials.

Advanced X-ray polarimeter design for nuclear resonant scattering.

This work presents the improvements in the design and testing of polarimeters based on channel-cut crystals for nuclear resonant scattering experiments at the 14.4 keV resonance of 57Fe. By using four asymmetric reflections at asymmetry angles of α1 = -28°, α2 = 28°, α3 = -28° and α4 = 28°, the degree of polarization purity could be improved to 2.2 × 10-9. For users, an advanced polarimeter without beam offset is now available at beamline P01 of the storage ring PETRAIII.

Photoionization of Astrophysically Relevant Atomic Ions at PIPE

We review recent work on the photoionization of atomic ions of astrophysical interest that has been carried out at the photon-ion merged-beams setup PIPE, a permanently installed end station at the XUV beamline P04 of the PETRA III synchrotron radiation source operated by DESY in Hamburg, Germany. Our results on single and multiple L-shell photoionization of Fe+, Fe2+, and Fe3+ ions, and on single and multiple K-shell photoionization of C−, C+, C4+, Ne+, and Si2+ ions are discussed in astrophysical contexts. Moreover, these experimental results bear witness of the fact that the implementation of the photon-ion merged-beams method at one of the world’s brightest synchrotron light sources has led to a breakthrough for the experimental study of atomic inner-shell photoionization processes with ions.