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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

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.

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. The main objectives of the AcE project are (i) the development of synthesis strategies for An(IV)-doped solid phases, (ii) understanding their associated structural and physical properties using combined modelling and experimental approaches and (iii) determining their performance after irradiation with particular regard to an assessment of their long-term stability, dissolution behavior, and suitability for An matrix incorporation. Recent results obtained for ZrO2, the main corrosion product of the Zircaloy cladding material surrounding nuclear fuel rods, will also be discussed. ZrO2 is monoclinic phase (P2(1)/c) at ambient conditions, and transforms into tetragonal (P4(2)/nmc) and cubic phases (Fm3 ̅m) at high temperatures of around 1200 °C and 2370 °C, respectively. However, particle size effects, the incorporation of foreign ions such as the actinides, as well as high radiation fields are known to also influence the stability fields of the polymorphs. A short overview of experimental studies conducted by the AcE partners, addressing both the ZrO2 bulk structure, irradiation-induced changes, as well as the An environment during and after such structural transformations, will be given.

Zirconia (ZrO2) is the primary corrosion product of the Zircaloy cladding material surrounding nuclear fuel rods [1]. It has also been envisioned as a ceramic host phase for specific high- level waste streams, immobilizing radionuclides and being able to become a protective barrier. In the case of doped ZrO2 matrices, a very high radiation tolerance has been reported, however, discrepancies exist regarding the role of the different structural polymorphs in the high radiation resistance. Ce has been used as a surrogate for Pu due to comparable chemical properties in the oxidation states +III and +IV, similar ionic radius, and its easier handling [2]. In the current study, phase transformations occurring in the ZrO2 material when doped with Ce(IV) and Gd(III), have been explored.

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. The main objectives of the AcE project are (i) the development of synthesis strategies for An(IV)-doped solid phases, (ii) understanding their associated structural and physical properties using combined modelling and experimental approaches and (iii) determining their performance after irradiation with particular regard to an assessment of their long-term stability, dissolution behavior, and suitability for An matrix incorporation. Recent results obtained for ZrO2, the main corrosion product of the Zircaloy cladding material surrounding nuclear fuel rods, in terms or actinide immobilization and radiation tolerance, will also be discussed. ZrO2 is monoclinic phase (P21/c) at ambient conditions, and transforms into tetragonal (P42/nmc) and cubic phases (Fm3 ̅m) at high temperatures of around 1200 °C and 2370 °C, respectively. However, particle size effects, the incorporation of foreign ions such as the actinides, as well as high radiation fields are known to also influence the stability fields of the polymorphs. A short overview of experimental studies conducted by the AcE partners, addressing both the ZrO2 bulk structure, irradiation-induced

Green bodies were prepared from dewatered coal flotation tailings and from mixtures comprising 70 wt% dewatered tailings/30 wt% glass and 50 wt% dewatered tailings/30 wt% glass/20 wt% coal mining waste. Porous bricks were prepared using H2O2 as foaming agent. Optimum results were obtained for all three formulations using 3 wt% H2O2. The green bodies were fired using different temperature profiles. The products obtained could easily be cut to standard dimensions. Addition of glass reduced the total shrinkage. Firing of the 70 wt% dewatered tailings/30 wt% glass formulation at 850 degrees C produced a porous reddish brick with a bulk density of 700 kg/m3 and a porosity of more than 70 wt%., Green bodies were prepared from dewatered coal flotation tailings and from mixtures comprising 70 wt% dewatered tailings/30 wt% glass and 50 wt% dewatered tailings/30 wt% glass/20 wt% coal mining waste. Porous bricks were prepared using H2O2 as foaming agent. Optimum results were obtained for all three formulations using 3 wt% H2O2. The green bodies were fired using different temperature profiles. The products obtained could easily be cut to standard dimensions. Addition of glass reduced the total shrinkage. Firing of the 70 wt% dewatered tailings/30 wt% glass formulation at 850 degrees C produced a porous reddish brick with a bulk density of 700 kg/m3 and a porosity of more than 70 wt%.