Search

The global energy system is in transition. It is attempting to reach net-zero greenhouse gas emissions by 2050. The systemic changes mean that the role of bioenergy will change. The potential of bioenergy to make a flexible contribution to the energy system is key for the achievement of global emission reduction ambitions and the functioning of the low-carbon energy system and economy. As the volume of sustainably available biomass resources is limited, defining the contributions from bioenergy to a low-carbon energy system and finding balances – and ideally synergies – between the different possible energy and climate system services that biomass can provide will be very important. The recognized system services include, among others, the flexible operation of bioenergy plants to integrate variable renewable energy sources and to provide negative carbon dioxide (CO2) emissions. Interest in flexible operation of bioenergy value chains, bioenergy with carbon capture and utilization as well as synergies with renewable hydrogen-based value chains has increased recently. The objective of this paper is to present a holistic definition of flexible bioenergy as a system service based on the work conducted in International Energy Agency (IEA) Bioenergy Technology Collaboration Programme's Task 44 Flexible Bioenergy and System Integration, and to provide some practical examples. The paper also presents the different bioenergy system services and considers their definitions and interactions, as this is important in energy system design. The definition of flexible bioenergy shows that the flexibility provision from bioenergy goes far beyond the traditional definition of providing short-term flexibility in the power sector. Indicators to demonstrate the value of services as well as further quantitative assessment of synergies and trade-offs are needed to valorize the different services from bioenergy and create viable business cases.

Crystalline materials such as monazite have been considered for the storage of radionuclides due to their apparent radiation stability. Understanding their structural chemical response to radiation damage is a key component of determining their suitability for this application. Herein, high resolution structural studies were performed on the monazite solid solution La1-CexPO4 (x = 0.25, 0.5, 0.75, 1) in order to understand the role of structural chemistry on irradiation stability. Ceramic samples were irradiated with 14MeV Au ions with 1014 ions/cm2 and 1015 ions/cm2 to simulate the recoil of daughter nuclei from the alpha decay of actinides. The extent of radiation damage was analysed in detail using scanning electron microscopy (SEM), Raman spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and high-energy-resolution fluorescence detection extended X-ray absorption fine structure (HERFD-EXAFS) spectroscopy. SEM and Raman revealed extensive structural damage as well as the importance of grain boundary regions, which appear to impede the propagation of defects. Both radiation-induced amorphisation and recrystallisation were studied by grazing incidence X-ray diffraction, highlighting the exceptional ability of monazite to remain crystalline at high fluences throughout the solid solution. Both, diffraction and HERFD-EXAFS experiments show that while atomic disorder is increased in irradiated samples compared to pristine ceramics, the short-range order was found to be largely preserved, facilitating recrystallisation. Crucially, this is consistent for all investigated samples, despite the chemical disorder introduced in the solid solution.

To mimic radiation damage by recoiling nuclei following alpha-decay, ceramics and single crystals of LaPO4 monazite doped with Eu(III) were irradiated with 14 MeV Au5+ ions at three different fluences. The crystallinity, local coordination environments, and topography of the samples were probed using numerous methods including grazing-incidence X-ray diffraction (GIXRD), vertical scanning interferometry (VSI), scanning electron microscopy (SEM), Raman, and luminescence spectroscopy. GIXRD data collected from the irradiated regions of the ceramics revealed fluence dependent amorphization. A similar level of amorphization was detected for samples irradiated with 5×1013 ions/cm2 (fluence, F1) and 1×1014 ions/cm2 (F2), while a slightly lower contribution to the scattering signal from the amorphous part was obtained for the sample irradiated with the highest fluence of 1×1015 ions/cm2 (F3). VSI showed clear swelling of entire grains at the highest ion fluence, while more localized damage to grain boundaries was detected for ceramic samples irradiated at the lowest fluence. Single crystal specimens showed no pronounced topography changes following irradiation. SEM backscattered electron images revealed that the ceramic irradiated at the highest fluence exhibited topological features indicative of grain surface melting or softening and displacement of grains. Finally, Raman and luminescence data showed a different degree of disorder in polycrystalline vs. single crystal samples. While changes to PO4 stretching and bending vibrations could be observed in the ceramics, these changes were more subtle or not present in the single crystals. The opposite was observed when probing the local Ln-O environment using Eu(III) luminescence, where the larger changes in terms of an elongation of the Eu-O (or La-O) bond and an increasing relative disorder with increasing fluence were observed only for the single crystals. The dissimilar trends observed in irradiated single crystals and ce

The long- and short- range structural chemistry of the C-type bixbyite compounds Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785 and Th0.45Nd0.37Ce0.18O1.815 is systematically examined using synchrotron X-ray powder diffraction (S-PXRD), high energy resolution fluorescence detection X-ray absorption near edge (HERFD-XANES) and extended absorption fine structure spectroscopy (EXAFS) measurements supported by electronic structure calculations. S-PXRD measurements revealed the title compounds all form classical C-type bixbyite structures in space group Ia3 ̅ that have disordered cationic crystallographic sites with further observation of characteristic superlattice reflections corresponding to oxygen vacancies. Despite the occurrence of oxygen vacancies, HERFD-XANES measurements on the Ce L3-edge revealed that Ce incorporates as Ce+4 into the structures but involves significant local distortion akin to cluster behavior and loss of nearest-neighbors. In comparison, HERFD-XANES measurements on the Nd+3 L3-edge supported by electronic structure calculations reveal that Nd+3 adopts a local coordination environment similar to the long-range C-type structure whilst providing charge balancing for the formation of oxygen defects. Th L3-edge EXAFS analysis reveals shorter average Th-O distances in the title compounds in comparison to pristine ThO2 in addition to shorter Th-O and Th-Ce distances compared to Th-Th or Ce-Ce in corresponding F-type binary oxides (ThO2 and CeO2). These distances are further found to decrease with the increased Nd content of the structures despite simultaneous observation of the overall lattice structure progressively expanding. Linear combination calculations of the M-O bond lengths are used to explain these observations, where the role of oxygen defects, via Nd+3 incorporation, induces local bond contraction and enhanced Th+4 cation valence leading to the observed increased lattice expansion with progressive Nd+3 incorporation. Overall, the inves

Ce-doped yttria-stabilized zirconia (YSZ) and pure YSZ phases were subjected to irradiation with 14 MeV Au ions. The irradiation studies were performed to simulate long-term structural and microstructural damage due to self-irradiation in YSZ phases hosting alpha-active radioactive species. It was found that both the Ce-doped YSZ and YSZ phases were rather tolerant to irradiation at high ion fluences and the bulk crystallinity was well preserved. Nevertheless, local microstrain increased in all the studied compounds after the irradiation, with the Ce-doped phases being less affected than pure YSZ. Doping with cerium ions increased the microstructural stability of YSZ phases through a possible reduction in the mobility of oxygen atoms, which limits the formation of structural defects. Doping of YSZ with tetravalent actinide elements is expected to have a similar effect. Thus, YSZ phases are promising for the safe long-term storage of radioactive elements. Using synchrotron radiation diffraction, measurements of the thin irradiated layers of the Ce-YSZ and YSZ samples were performed in grazing incidence (GI) mode. A corresponding module for measurements in GI mode was developed at ROBL and relevant technical details of sample alignment and data collection are also presented.

Zirconia is largely studied because of its ability to incorporate lanthanides and actinides; this has been one of the strategies adopted to try to immobilize ions from High-Level Radioactive Waste (HLW). Furthermore, cerium is often used as a surrogate for plutonium due to its analogous chemical properties1. In this study, zirconia samples with different Ce concentrations were syntehsized via the co-precipitation route. A small amount of Eu as co-dopants was added during synthesis to enable luminescence spectroscopic analyses of the solids phases2. Six zirconia compositions doped with 15 to 80 mol%Ce were prepared. The phase composition was evaluated by site selective luminescence spectroscopy (ss-TRLFS) and Synchrotron Powder X-Ray Diffraction. The latter method showed, that more than one phase coexists in all samples with concentrations lower than 80 mol% Ce. The tetragonal phase is predominant until 30 mol% Ce-doping, and above this concentration, a metastable phase (t’’) starts becomes dominant. The phase transformation can also be deduced from the coordination environment of europium, showing a small band at 583 nm, characteristic for the monoclinic phase, and another one at around 581.1 nm for Eu incorporated in the tetragonal phase. The systematic shift of this signal to shorter wavelengths points toward a lengthening of the Eu-O bonds with increasing Ce concentration, as the unit cell becomes systematically larger. The excitation peaks are clearly broader for the samples with predominantly t’’-ZrO2, which points toward a less ordered environement. This is in agreement with the hypothesized displacement of oxygen atoms from ideal (cubic) crystallographic positions, in this metastable (transition) phase.

This contribution provides an overview of a current research network funded by the German Federal Ministry of Education and Research (BMBF), entitled “Fundamental investigations of actinide immobilization by incorporation into solid phases relevant for final disposal” – AcE. The AcE project aims at understanding the incorporation and immobilization of actinides (An) in crystalline, repository-relevant solid phases, such as zirconia (ZrO2) and UO2, but also in zircon (ZrSiO4), pyrochlores (Ln2Zr2O7) and orthophosphates of the monazite type (LnPO4), which may find use as host matrices for the immobilization and safe disposal of high-level waste streams. Recent studies by the AcE-project consortium, addressing the structure, properties, and the radiation tolerance of monazites and Zr(IV)-based solid phases containing actinides or their surrogates from the lanthanide series will be presented. Material synthesis strategies in the AcE project have aimed at generating single-phase solid solutions in the form of polycrystalline powders, dense ceramics, and single crystals. Structural studies using powder X-ray diffraction at ambient conditions, but also at high temperatures and pressures have been complemented with a wide range of microscopic and spectroscopic techniques to address differences between the host- and dopant environments in the solid matrices at ambient and extreme conditions. The radiation tolerance of the synthetic solid phases have been investigated by combining external heavy-ion irradiation of inactive Ln-doped materials and in situ self-irradiation of 241Am-doped Zr(IV)-phases with monoclinic, cubic defect fluorite and pyrochlore structures. The latter experiments have been conducted in joint efforts with the Joint Research Center in Karlsruhe within the ActUsLab programme.

Due to their applications in catalysis, energy storage or biomedicine, many studies report synthesis and characterizations of CeO2 NPs and intensively use X-ray sources for characterization. In this study, we report a comprehensive interpretation of X-ray measurements on CeO2 models with atomically resolved structure, namely oxo-hydroxo polynuclear Ce complexes. A set of Ce clusters with growing size (0.6 nm to 1.2 nm) and nuclearity (from 6 to 38 Ce atoms) were synthetized and characterized by single crystal XRD. The samples were then analyzed using HEXS and HERFD technics and compared to larger CeO2 NPs and bulk CeO2. Both spectroscopic methods reveal consistent trends as the particle grows or shrink from the set of molecular Ce-{n} clusters up to bulk CeO2. HEXS reveals a broadening in distribution for the short Ce-oxygen bonds for the small clusters. Concomitantly, the HERFD performed at the Ce LIII edge indicates a gradual splitting of the cerium 5d states as the particles become more CeO2 like. From the crystallographic determination of the clusters structure, atomically resolved Ce LIII edge simulation were undertaken. These simulations allow to isolate structural and electronic properties for individual Ce sites within clusters and evidence the great difference between surface and core Ce atoms. It also shows how a combination of simulations from different sites results in the accurate reproduction of the corresponding experimental data. This approach based on clusters atomic sites was then successfully extended to model larger CeO2 NPs Ce LIII edge HERFD spectra. By linking atomically resolved structures to nanoparticles and bulk material using crystallography, X-ray technics and simulation, this work extends the knowledge on cerium oxide nanomaterial and supports a better understanding and predictability of their crystalline and electronic structure

Swelling is the most fundamental property of graphite oxides (GO). Here, a structural study of Brodie graphite oxide (BGO) swelling in a set of long chain 1-alcohols (named C11 to C22 according to the number of carbons) performed using synchrotron radiation X-ray diffraction at elevated temperatures is reported. Even the longest of tested alcohols (C22) is found to intercalate BGO with enormous expansion of the interlayer distance from ≈6Å up to ≈63Å, the highest expansion of GO lattice ever reported. Swelling transitions from low temperature alpha-phase to high temperature beta-phase are found for BGO in all alcohols in the C11–C22 set. The transitions correspond to decrease of inter-layer distance correlating with the length of alcohol molecules, and change in their orientation from perpendicular to GO planes to layered parallel to GO (Type II transitions). These transitions are very different compared to BGO swelling transitions (Type I) found in smaller alcohols and related to insertion/de-insertion of additional layer of alcohol parallel to GO. Analysis of general trends in the whole set of 1-alcohols (C1 to C22) shows that the 1-alcohol chain length defines the type of swelling transition with Type I found for alcohols with C<10 and Type II for C>10.

Cr-doped UO2 is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in the bulk material has prevented acquisition of an unequivocal understanding of the redox chemistry and mechanism for incorporation of Cr in the UO2 matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near energy structure and extended X-ray absorption fine structure spectroscopic measurements to examine Cr-doped UO2 single crystal grains and bulk material. Ambient condition measurements of the single crystal grains, which have been mechanically extracted from bulk material, indicated Cr is incorporated substitutionally for U+4 in the fluorite lattice as Cr+3 with formation of additional oxygen vacancies. Bulk material measurements reveal the complexity of Cr states, where metallic Cr (Cr0) and oxide related Cr+2 and Cr+32O3 were identified and attributed to grain boundary species and precipitates, with concurrent (Cr+3xU+41-x)O2-0.5x lattice matrix incorporation. The deconvolution of chemical states via crystal vs. powder measurements enables the understanding of discrepancies in literature whilst providing valuable direction for safe continued use of Cr-doped UO2 fuels for nuclear energy generation.

The strongly intended transition of global energy systems to reach net-zero GHG emissions by mid-century means that the role of bioenergy will change. The potential of bioenergy to contribute to the energy system in flexible modes is key for the fulfilment of global emission reduction ambitions and the functioning of the low-carbon energy system and economy. As sustainably available biomass resources are limited in volumes, finding balances - and ideally, synergies - between the different possible energy and climate system services will be highly important. Preliminary valorisation framework, developed by IEA Bioenergy TCP Task 44 Flexible Bioenergy and System Integration, presents considerations on system services, interactions and synergies between the services, and Key Performance Indicators (KPIs) to assess the value of system services.

Experimental and fitted EPR data of Cr-UO2 single crystal grains, EXAFS data Cr-UO2 single crystal grain and powder with Cr redox standards, XANES data Cr-UO2 single crystal grain and powder with Cr redox standards

Increased reactivity of radiation-damaged quartz in the alkaline pore water of concrete and its role in radionuclide transport is a subject that is becoming increasingly important as nuclear power plants (NPPs) around the world reach end-of-life. Quartz contributes more than half the weight of most concretes and up to 40 % of the total radioactive waste volume associated with the dismantling of an NPP. The gamma-emitting radionuclides are the major contributors to the radiation dose rate in the concrete biological shield in the intermediate term after NPP shut-down. The appreciable activity and associated half-lives of these radionuclides pose a problem not only during the safe dismantling of NPPs, but also in terms of processing the concrete to reduce the active waste volume for final disposal in a repository. While thermal neutrons are captured by atomic nuclei according to their thermal neutron cross-sections, fast neutrons undergo collision cascades, which cause defects in the structure of materials. The concentration of defects accumulates as a function of neutron energy and fluence. The high covalency and the density of Si-O bonds in tectosilicates, primarily quartz, followed by feldspars, makes these minerals very susceptible to radiation damage. In this study, two inactive concrete powder samples were placed inside an instrumentation channel passing through the first biological shielding of an operating German NPP, respectively for a half- and a full fuel cycle. Using a plant-specific 3D-reactor model in conjunction with Monte Carlo neutron transport calculations, neutron fluences at the sample positions and the resulting gamma activities are calculated. We compare the measured and calculated activities of the gamma-emitting radionuclides Synchrotron X-ray powder diffractometry was used to examine structural changes on sub-nanoscale. The local structure of the silicate aggregate minerals was investigated by solid-state magic angle spinning nuclear magnetic r

Long-living radiotoxic isotopes present in spent nuclear fuel (SNF) requires procedures of complete immobilization of these species. Incorporation of the corresponding elements on atomic level into robust host crystalline matrices is one way to secure SNF during long-term underground storage. Derivatives of zirconia, ZrO2, are promising materials for these applications since these phases are known to remain structurally stable in geological cycles of up to 109 years [1]. The candidate host matrix must provide a sufficient solubility limit for radiotoxic elements, which is studied initially. Afterwards, structural stability of these phases against irradiation and leaching are established in order to asses possible discharge of the incorporated radioactive elements over a long-time scale. In this work we studied systematically structural behaviour of ZrO2-based materials incorporated with Th4+ and Ce4+ under extreme conditions of temperature (T) and pressure (P) in order to simulate experimentally possible phase evolution in conditions of underground storage. In situ synchrotron radiation powder diffraction experiments under ambient and extreme conditions were performed at the HZDR ROBL BM20 beamline at ESRF, Grenoble, France [2]. It was found that cubic YSZ phases could dissolve 20% more of Th atoms compared to their tetragonal analogues. In situ T-dependent diffraction studies on radionuclide surrogate tetragonal and cubic Ce-YSZ series in a RT-1150 K range revealed excellent phase stabilities. No discharge of guest Ce4+ ions was observed. Nevertheless, application of external pressure on tetragonal Ce-YSZ phase induced transition towards a higher cubic symmetry around the P ~ 8.5 GPa. Remarkably, occupancy of Ce4+ remains stable throughout the transition. This together with T-dependent data indicates excellent affinity of guest Ce atoms with the YSZ structures. Thus, we suggest in situ studies under extreme conditions as a part of standard protocol to validate phas