Synchrotron Radiation Facility Research Articles

Existence of density inhomogeneity of liquid Te associated with liquid–liquid phase transition

We performed small-angle x-ray scattering measurements of liquid Te using a synchrotron radiation facility and observed maximum scattering intensity near 620 K in the supercooled region (melting temperature 723 K). This indicates that density inhomogeneity exists in liquid Te, and the fact that this temperature coincides with the temperature at which the specific heat, sound velocity, and thermal expansion coefficient reach their maxima means that this density inhomogeneity is the cause of these thermodynamic anomalies. The thermodynamic anomalies in liquid Te had already been shown in the 1980s to be comprehensively explained by the inhomogeneity associated with the continuous liquid–liquid phase transition (LLT), but direct experimental evidence for the existence of the inhomogeneity had not been obtained. The present results, together with those already obtained for mixture systems (Te–Se, Te–Ge), indicate the existence of inhomogeneity associated with LLT in liquid Te systems, and strongly support the model. Recently, similar maximum scattering intensity has also been observed in supercooled liquid water, which exhibits thermodynamic anomalies similar to those of Te, indicating the universality of the inhomogeneous model or LLT scenario to explain the thermodynamics of such ‘anomalous liquids’. Further development of the LLT scenario is expected in near future.

Off-energy operation for the Extremely Brilliant Source at the European Synchrotron Radiation Facility

The European Synchrotron Radiation Facility Extremely Brilliant Source (ESRF-EBS) is the first fourth generation 6 GeV storage ring (SR) light source making use of the hybrid multibend achromat lattice, reaching a natural horizontal emittance of 140 pm rad. Further, reducing the horizontal emittance would provide a more brilliant and a higher quality photon source for the EBS users. One way of achieving this is to operate the SR off-energy. The first approach reduces the electron beam energy by −1%, which gives a 121 pm rad natural horizontal emittance. To fulfill operation requirements, the full ring had to be rematched, including both the quadrupoles and the sextupoles in the linear optics correction. The off-energy settings are then tested in the SR in terms of lifetime, injection efficiency, and operability. Published by the American Physical Society 2024

Synchrotron x-ray spectra characterisation for radiation therapy applications at the ESRF - ID17 biomedical beamline

Objective. Radiation therapy requires reliable dosimetry protocols to deliver successful treatments with high accuracy and precision. In this context, accurate knowledge of the beam’s energy spectra is mandatory. The goal of this study was to validate the synchrotron x-ray spectrum of the ID17 beamline at the European Synchrotron Radiation Facility (ESRF). The modification of the synchrotron storage ring and beamline in recent years necessitates a new characterisation of the radiation spectra of the ID17 beamline. The validated spectra will be a starting point for possible future clinical applications. Approach. The half value layer method was used to measure the attenuation of the x-ray spectrum in Al and Cu. Experimental data was validated against theoretical data produced using OASYS; an in-house developed software for calculating beamline spectra. Two different spectral configurations, ‘conventional’ and ‘clinical’, were investigated. The characterised spectra were used to perform dosimetric validation of depth dose profiles measured in a water-equivalent phantom. The dose profile was measured using two different detectors and compared with calculations generated using two different Monte Carlo algorithms. Main results. The results showed good agreement between measured and predicted half value layers, with differences of less than 1% in most cases. Excellent dosimetric agreement to within 3% was obtained, an agreement that satisfies the requirements in conventional radiotherapy for approvable treatment planning. Significance. Accurate spectra have been defined and validated for the ESRF—ID17 Biomedical beamline. The validated spectra can be used as input for future dosimetric studies and treatment planning systems in the context of preclinical studies and possible future clinical trials.

Direct Work Function Measurement Using In-situ APXPS and Its Application on Copper Oxidation Process.

The work function (WF) measurement plays a critical role in engineering energy materials and energy devices. However, the ultra-high vacuum (UHV) environments of photoemission method limit the practical application for absolute work function measurements of materials, especially under complex working conditions. To understand the energy level of materials under complex chemical environments, the in-situ measurements of work function is necessary in complex metal/semiconductor system for various application. In this paper, we describe the utilization of ambient pressure X-ray photoemission spectroscopy (APXPS) with utilization of low photon energy X-ray for absolute WF measurements at BL02B of the Shanghai Synchrotron Radiation Facility. We herein present the WF measurement during oxygen adsorption on Pt(111) and oxidation of Cu(111) in ambient oxygen environment as demonstration of the APXPS capability for WF measurement. After oxygen chemisorption on Pt and formation of Cu2O, the WF will increase. This is due to charge transfer from metal to chemisorbed oxygen atoms. After the formation of bulk Cu2O and CuO, the WF value almost remain at ~5.5 eV. We believe the direct measurement of absolute work function via APXPS could help bridge the gap between the physical properties and the surface chemical species for metal/semiconductor materials.

Development of an x-ray polarimeter at the SOLEIL synchrotron.

Synchrotron radiation facilities provide highly polarized x-ray beams across a wide energy range. However, the exact type and degree of polarization vary according to the beamline and experimental setup. To accurately determine the angle and degree of linear polarization, a portable x-ray polarimeter has been developed. This setup consists of a silicon drift detector that rotates around a target made of high-density polyethylene. The imprint generated in the angular distribution of scattered photons from the target at a 90-degree angle between the incident x-rays and detector has been exploited to determine the beam polarization. Measurements were conducted at the GALAXIES beamline of the SOLEIL synchrotron. The expected angular distribution of the scattered photons for a given beam polarization was obtained through simulations using the Geant4 simulation toolkit. An excellent agreement between simulations and the collected data has been obtained, validating the setup and enabling a precise determination of the beam polarization.

Exploring the sintering behavior of a complex ceramic powder system using in-situ X-ray nano-tomography

As a typical example of constrained sintering, the behavior of a complex ceramic powder system with multi-heterogeneities has been investigated. This powder system comprises inherent imperfections as well as rigid inclusions that act as constraints to densification. The sintering process of the system was monitored by in-situ X-ray nano-tomography at the European Synchrotron Radiation Facility (ESRF). This technique enables three-dimensional (3D) imaging of the microstructure with a voxel size of 25nm. The images obtained reveal the distribution of imperfections in the powder system, such as particle aggregation and pore segregation in and around them. The subsequent in-situ evaluations show the evolution of the microstructure in the presence of inclusions. The study addresses the questions pertaining to the effect of the added constraints, the consequent crack generation and their implication on the final densification of the material.

Novel high-pressure/high-temperature reactor cell for in situ and operando x-ray absorption spectroscopy studies of heterogeneous catalysts at synchrotron facilities.

This paper presents the development of a novel high-pressure/high-temperature reactor cell dedicated to the characterization of catalysts using synchrotron x-ray absorption spectroscopy under operando conditions. The design of the vitreous carbon reactor allows its use as a plug-flow reactor, monitoring catalyst samples in a powder form with a continuous gas flow at high-temperature (up to 1000 °C) and under high pressure (up to 1000bar) conditions, depending on the gas environment. The high-pressure/high-temperature reactor cell incorporates an automated gas distribution system and offers the capability to operate in both transmission and fluorescence detection modes. The operando x-ray absorption spectroscopy results obtained on a bimetallic InCo catalyst during CO2 hydrogenation reaction at 300 °C and 50bar are presented, replicating the conditions of a conventional microreactor. The complete setup is available for users and permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental (CRG-FAME) sciences and French Absorption spectroscopy beamline in Material and Environmental sciences at ultra-high dilution (FAME-UHD) beamlines (BM30 and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

X-ray storage tracks characteristics for Ag-doped phosphate glass based on radio-photoluminescence

Ag-doped phosphate glass (Ag-PG) is an excellent X-ray image storage material applied for recording X-ray tracks. In this work, we used Geant4 software to simulate the energy deposition attenuation and 2D/3D storage tracks characteristics of Ag-PG. The influence of the secondary particles generated by the interaction between X-rays and Ag-PG was analyzed. The storage cutoff depth of Ag-PG was verified at the Shanghai Synchrotron Radiation Facility (SSRF). The results show that the optical transmittance is slightly decreased after X-ray irradiation. The cutoff depth is only 200 μm for complete absorption, when the X-ray energy is 5 keV. The deposited energy is attenuated by 19.8% at the depth of 900 μm, when the X-ray energy is 30 keV. The distribution of deposited energy is primarily influenced by the attenuation of secondary electrons generated by the interaction between X-rays and Ag-PG. Furthermore, the 2D/3D models show that the storage depth is not significantly affected by different doses at the same X-ray energy. The low diffusion of the tracks spread plays a crucial role in achieving high spatial resolution. The storage cutoff depth in Ag-PG is approximately 10 mm at 20 keV. This has been successfully verified by SSRF, and it holds great significance for high-resolution imaging and quantitative storage of X-ray images in Ag-PG.

Preparation and measurement of an x-ray Laue-type monochromator based on a WSi2/Si multilayer

The Laue-type multilayer monochromator (LMM) is a promising optical element with a small size and high efficiency in a synchrotron radiation facility. By the dynamical diffraction theory, using DC magnetron sputtering technology, an LMM with a total thickness of 47 µm and a periodic thickness of 4.7 nm WSi2/Si multilayer at 26 keV is designed and fabricated. During the preparation, the total number of layers is up to 20000, and every 300th layer of Si is replaced by WSi2 as the marker, so the multilayer is divided into 67 areas. The cross section of the multilayer is measured by a scanning electron microscope (SEM), and the marker region thickness error is 0.28% (RMS). The diffraction test experiment of the LMM is carried out at the Shanghai synchrotron radiation facility (SSRF). The 1st-order peak angle is 5.05 mrad, and the efficiency is 75.0%, which is close to the theoretical calculation result of 5.1 mrad and 79.1%. The Darwin width of the LMM is 0.17 mrad which is equal to the theoretical calculation. Based on the Bragg’s diffraction equation, the energy resolution (ΔE/E) is 3.3%.

Upgrade of crystallography beamline BL19U1 at the Shanghai Synchrotron Radiation Facility

BL19U1, an energy-tunable protein complex crystallography beamline at the Shanghai Synchrotron Radiation Facility, has emerged as one of the most productive MX beamlines since opening to the public in July 2015. As of October 2023, it has contributed to over 2000 protein structures deposited in the Protein Data Bank (PDB), resulting in the publication of more than 1000 scientific papers. In response to increasing interest in structure-based drug design utilizing X-ray crystallography for fragment library screening, enhancements have been implemented in both hardware and data collection systems on the beamline to optimize efficiency. Hardware upgrades include the transition from MD2 to MD2S for the diffractometer, alongside the installation of a humidity controller featuring a rapid nozzle exchanger. This allows users to opt for either low-temperature or room-temperature data collection modes. The control system has been upgraded from Blu-Ice to MXCuBE3, which supports website-mode data collection, providing enhanced compatibility and easy expansion with new features. An automated data processing pipeline has also been developed to offer users real-time feedback on data quality.

The influence of cation exchange on the possible mechanism of erionite toxicity: A synchrotron-based micro-X-ray fluorescence study on THP-1-derived macrophages exposed to erionite-Na

Fibrous erionite is the only zeolite classified as Group 1 carcinogen by the International Agency for Research on Cancer (IARC). Carcinogenesis induced by erionite is thought to involve several factors as biopersistence, the iron role and cation exchange processes. To better understand these mechanisms, a detailed investigation at the micro scale was performed, collecting elemental information on iron and cation release and their distribution in biological systems by synchrotron micro-X-ray fluorescence mapping (SR-micro-XRF) and synchrotron micro-X-ray absorption spectroscopy (SR-micro-XANES) at the TwinMic beamline (Elettra synchrotron) and at the ID21 beamline of the European Synchrotron Radiation Facility (ESRF). By microscopy and chemical mapping, highly detailed maps of the chemical and morphological interaction of biological systems with fibres could be produced. In detail, THP-1 cell line derived macrophages, used as in vitro model, were analysed during erionite-Na phagocytosis at different time intervals, after single dose exposure. For comparison, cellular fluorescent probes were also used to evaluate the intracellular free sodium and calcium concentrations. Synchrotron analyses visualised the spatial distribution of both fibre and mineral particle associated metals during the phagocytosis, describing the mechanism of internalisation of erionite-Na and its accessory mineral phases. The intracellular distribution of metals and other cations was mapped to evaluate metal release, speciation changes and/or cation exchange during phagocytosis. The fluorescent probes complemented microchemical data clarifying, and confirming, the cation distribution observed in the SR-micro-XRF maps. The significant cytoplasmic calcium decrease, and the concomitant sodium increase, after the fibre phagocytosis seemed due to activation of plasma membrane cations exchangers triggered by the internalisation while, surprisingly, the ion-exchange capacity of erionite-Na could play a minor role in the disruption of the two cations intracellular homeostasis. These results help to elucidate the role of cations in the toxicity of erionite-treated THP-1 macrophages and add knowledge to its carcinogenicity process.

Edge-illumination spectral phase-contrast tomography

Following the rapid, but independent, diffusion of x-ray spectral and phase-contrast systems, this work demonstrates the first combination of spectral and phase-contrast computed tomography (CT) obtained by using the edge-illumination technique and a CdTe small-pixel (62 μm) spectral detector. A theoretical model is introduced, starting from a standard attenuation-based spectral decomposition and leading to spectral phase-contrast material decomposition. Each step of the model is followed by quantification of accuracy and sensitivity on experimental data of a test phantom containing different solutions with known concentrations. An example of a micro CT application (20 μm voxel size) on an iodine-perfused ex vivo murine model is reported. The work demonstrates that spectral-phase contrast combines the advantages of spectral imaging, i.e. high-Z material discrimination capability, and phase-contrast imaging, i.e. soft tissue sensitivity, yielding simultaneously mass density maps of water, calcium, and iodine with an accuracy of 1.1%, 3.5%, and 1.9% (root mean square errors), respectively. Results also show a 9-fold increase in the signal-to-noise ratio of the water channel when compared to standard spectral decomposition. The application to the murine model revealed the potential of the technique in the simultaneous 3D visualization of soft tissue, bone, and vasculature. While being implemented by using a broad spectrum (pink beam) at a synchrotron radiation facility (Elettra, Trieste, Italy), the proposed experimental setup can be readily translated to compact laboratory systems including conventional x-ray tubes.

A new experimental station for microbeam X-ray scattering at the SSRF BL10U1 beamline

Benefiting from the development of high-brilliance synchrotron radiation sources, microbeam X-ray scattering has become a well established scattering-based imaging technology. This article describes the newly constructed time-resolved microbeam small-angle X-ray scattering (µSAXS) experimental station at the BL10U1 beamline at the Shanghai Synchrotron Radiation Facility. The µSAXS endstation provides SAXS/WAXS measurements with a 10 µm hard X-ray beam and a flux of ∼1012 photons s−1. A multi-axis sample stage, an on-axis viewer and in situ experimental apparatus are incorporated to facilitate multi-method scientific experiments in various material fields. As scientific examples, this article explores 1D tomography, 2D mapping and tomographic sectioning based on X-ray scattering to investigate the micro–nanostructures of polymer fiber, spherulite and bamboo samples.

Multilayer Kirkpatrick-Baez focusing mirrors with phase compensation for sub-20 nm focusing at the hard X-ray nanoprobe beamline of SSRF

The hard X-ray nanoprobe beamline is the first beamline to take advantage of the full coherent beam to attain the nanoscale focusing at the Shanghai Synchrotron Radiation Facility (SSRF). Here we introduce the beamline and specially go over the features of the multilayer Kirkpatrick-Baez focusing system and its supporting phase compensator system. The performance and stability of the phase compensator are also put to the test. By using the speckle scanning metrology, the wavefront of a focused beam was characterized and intensity distribution near the focus was reconstructed. The focusing performance was greatly enhanced by two phase compensations based on a global optimization technique, and a two-dimensional focal spot of 26 nm × 17 nm was achieved and maintained with good stability.

In situ X-ray imaging and numerical modeling of damage accumulation in C/SiC composites at temperatures up to 1200 °C

Carbon fiber reinforced silicon carbide matrix composites (C/SiC) have emerged as key materials for thermal protection systems owing to their high strength-to-weight ratio, high-temperature durability, resistance to oxidation, and outstanding reliability. However, manufacturing defects deteriorate the mechanical response of these composites under extreme thermal-force coupling conditions, prompting significant research attention. This study demonstrates a customized in situ loading device compatible with synchrotron radiation facilities, enabling high spatial and temporal resolution recording of internal material damage evolution and failure behavior under thermal-force coupling conditions. Infrared thermal radiation units in a confocal configuration were used to create ultra-high-temperature environments, offering advantages of compactness, rapid heating, and versatility. In situ tensile tests were conducted on C/SiC samples in a nitrogen atmosphere at both room temperature and 1200 °C. The high-resolution image data demonstrate various failure phenomena, such as matrix cracking and pore linkage. Image-based finite element simulations indicate that the temperature-dependent variation of the failure mechanism is attributable to thermal residual stresses and defect-induced stress concentrations. This work seamlessly integrates extreme mechanical testing methods with in situ observation techniques, providing a comprehensive solution for accurately quantifying crack initiation, pore connection, and failure behavior of C/SiC composites.

Research and optimization of flow-induced vibrations in a water-cooled monochromator.

To enhance the stability of the water-cooled double-crystal monochromator used at the BL17B beamline of the Shanghai Synchrotron Radiation Facility (SSRF), a study was conducted to optimize its cooling system's flow-induced vibration. Through simulation and experimental verification, the researchers analyzed the vibration mechanism and implemented improvement measures. The results indicate that the elastic bellows greatly amplify flow-induced vibration, transmitting it to the first-crystal. By positioning the bellows closer to the crystal, the relative pitch angular vibration of the double-crystal was reduced by 17.5%, and the roll angular vibration decreased by 6.1%. Furthermore, changing the flow rate from 3 to 2.4 l/min further diminished the relative pitch angular vibration by 6.0% and the roll angular vibration by 7.9%. By effectively reducing flow-induced vibration in the water-cooled double-crystal monochromator, equipment stability is enhanced, and the relative angular vibration of the double-crystal has been reduced. This research provides a valuable method and approach for optimizing the stability of the monochromator and related equipment.

Crystallographic Data Collection Using a Multilayer Monochromator on an Undulator Beamline at the Shanghai Synchrotron Radiation Facility

To resolve photons hungry for weak diffraction samples by the crystallographic method, a double-multilayer monochromator (DMM) was employed on an undulator beamline (BL17UM) at the Shanghai Synchrotron Radiation Facility (SSRF) to provide a focused sub-micron beam with high brightness for macromolecular crystallography experiments. High-quality crystallographic datasets from model protein crystal samples were collected and processed by an existing crystallographic program for structure solution and refinement. The data quality was compared with datasets from a normal silicon crystal monochromator to evaluate the bandwidth of the DMM effect on these crystallographic data. This experiment demonstrates that multilayer optics on an undulator beamline may play a valuable role in satisfying the demands of structure-related research, which requires novel methods.

Quantifying bunch-mode influence on photon-counting detectors at SPring-8.

Count-loss characteristics of photon-counting 2D detectors are demonstrated for eight bunch-modes at SPring-8 through Monte Carlo simulations. As an indicator, the effective maximum count rate was introduced to signify the X-ray intensity that the detector can count with a linearity of 1% or better after applying a count-loss correction in each bunch-mode. The effective maximum count rate is revealed to vary depending on the bunch-mode and the intrinsic dead time of the detectors, ranging from 0.012 to 0.916 Mcps (megacounts per second) for a 120 ns dead time, 0.009 to 0.807 Mcps for a 0.5 µs dead time and 0.020 to 0.273 Mcps for a 3 µs intrinsic detector dead time. Even with equal-interval bunch-modes at SPring-8, the effective maximum count rate does not exceed 1 Mcps pixel-1. In other words, to obtain data with a linearity better than 1%, the maximum intensity of X-rays entering the detector should be reduced to 1 Mcps pixel-1 or less, and, in some cases, even lower, depending on the bunch-mode. When applying count-loss correction using optimized dead times tailored to each bunch-mode, the effective maximum count rate exceeds the values above. However, differences in the effective maximum count rate due to bunch-modes persist. Users of photon-counting 2D detectors are encouraged to familiarize themselves with the count-loss characteristics dependent on bunch-mode, and to conduct experiments accordingly. In addition, when designing the time structure of bunch-modes at synchrotron radiation facilities, it is essential to take into account the impact on experiments using photon-counting 2D detectors.

Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0eV.

Unravelling the role of iron and manganese oxides in colouring Late Antique glass by micro-XANES and micro-XRF spectroscopies

This research aims to understand colouring technologies in 5th–7th centuries glass imported to Atlantic Britain by correlating the iron (Fe) and manganese (Mn) ratios and oxidation states with colour. Despite having a similar matrix chemical composition and concentrations of Fe and Mn oxides, these vessels display different colours (from green to yellow/amber, sometimes with purple streaks). Colour changes can be induced by controlling the reduction-oxidation reactions that occur during glass production, which are influenced by the raw materials, furnace and melt atmosphere, and recycling. To evaluate these parameters, reference glasses were prepared, following the composition of Late Antique archaeological glass recovered from Tintagel (UK) and Whithorn (UK). A corpus of archaeological and experimental glass samples was analysed using bulk Fe and Mn K-edge x-ray absorption near edge structure (XANES) spectroscopy, micro-XANES and micro x-ray fluorescence (μ-XRF) at beamline ID21, at the European Synchrotron Radiation Facility. Fe and Mn XANES spectra of the archaeological glass indicate that Fe and Mn are in a similar oxidation state in all the yellow samples, predominantly Fe3+ and Mn2+. No detectable difference in Mn and Fe oxidation state occurs in the purple streaks compared to the yellow glass bulk but μ-XRF maps of the distribution of Fe and Mn show that Mn is more concentrated in the purple streaks. This indicates that the purple colour of the streaks is mainly due to a higher Mn/Fe ratio and persistence of more oxidised manganese in the purple areas, even though it is difficult to detect. Many archaeological fragments appear pale green in transmitted light but amber in reflected light. XANES studies detected the presence of surface layers where manganese is more oxidised. This layer is believed to scatter transmitted and reflected light differently and might be responsible for the optical features of the archaeological glass.