High thermal neutron flux effects on structural and macroscopic properties of alkali-borosilicate glasses used as neutron guide substrate

The behaviour of four alkali-borosilicate glasses under homogeneous thermal neutron irradiation has been studied. These materials are used for the manufacturing of neutron guides which are installed in most facilities as devices to transport neutrons from intense sources such as nuclear reactors or spallation sources up to scientific instruments. Several experimental techniques such as Raman, NMR, SANS and STEM have been employed in order to understand the rather different macroscopic behaviour under irradiation of materials that belong to a same glass family. The results have shown that the remarkable glass shrinking observed for neutron doses below 0.5 · 10 18 n/cm 2 critically depends upon the presence of domains where silicate and borate network do not mix

Discovery of a maximum damage structure for Xe-irradiated borosilicate glass ceramics containing powellite

In order to increase the waste loading efficiency in nuclear waste glasses, alternate glass ceramic (GC) materials are sought that trap problematic molybdenum in a water-durable CaMoO4 phase within a borosilicate glass matrix. In order to test the radiation resistance of these candidate wasteforms, accelerated external radiation can be employed to replicate long-term damage. In this study, several glasses and GCs were synthesized with up to 10 mol% MoO3 and subjected to 92 MeV Xe ions with fluences ranging between 5 × 10^12 to 1.8 × 10^14 ions/cm2. The main mechanisms of modification following irradiation involve: (i) thermal and defect-assisted diffusion, (ii) relaxation from the ion's added energy, (iii) localized damage recovery from overlapping ion tracks, and (iv) the accumulation of point defects or the formation of voids that created significant strain and led to longer-range modifications. Most significantly, a saturation in alteration could be detected for fluences greater than 4 × 10^13 ions/cm2, which represents an average structure that is representative of the maximum damage state from these competing mechanisms. The results from this study can therefore be used for long-term structural projections in the development of more complex GCs for nuclear waste applications.EPSRC (Grant No. EP/K007882/1

Self-healing capacity of nuclear glass observed by NMR spectroscopy

Safe management of high level nuclear waste is a worldwide significant issue for which vitrification has been selected by many countries. There exists a crucial need for improving our understanding of the ageing of the glass under irradiation. While external irradiation by ions provides a rapid simulation of damage induced by alpha decays, short lived actinide doping is more representative of the reality. Here, we report radiological NMR experiments to compare the damage in International Simplified Glass (ISG) when irradiated by these two methods. In the 0.1 mole percent 244Cm doped glass, accumulation of high alpha decay only shows small modifications of the local structure, in sharp contrast to heavy ion irradiation. These results reveal the ability of the alpha particle to partially repair the damage generated by the heavy recoil nuclei highlighting the radiation resistance of nuclear glass and the difficulty to accurately simulate its behaviour by single ion beam irradiations

Molecular dynamics simulation of radiation damage in glasses

Molecular dynamics simulations of the ballistic effects arising from displacement cascades in glasses have been investigated in silica and in a SiO 2 -B 2 O 3 -Na 2 O glass. In both glasses the T-O-T′ angle (where T and T′ are network formers) diminishes, despite radiation causes opposite effects: while the ternary glass swells and silica becomes denser. We show that radiation-induced modifications of macroscopic glass properties result from structural change at medium/range, reflecting an increasing disorder and internal energy of the system. A local thermal quenching model is proposed to account for the effects of ballistic collisions. The core of a displacement cascade is heated by the passage of the projectile, then rapidly quenched, leading to a process that mimics a local thermal quenching. The observed changes in both the mechanical and structural properties of glasses eventually reach saturation at 2 10 18 α/g as the accumulated energy increases. The passage of a single projectile is sufficient to reach the maximum degree of damage, confirming the hypothesis postulated in the swelling model proposed by J.A.C. Marples

Impacts of composition and beta irradiation on phase separation in multiphase amorphous calcium borosilicates

Borosilicate glasses for nuclear waste applications are limited in waste loading by the precipitation of water-soluble molybdates. In order to increase storage efficiency, new compositions are sought out that trap molybdenum in a water-durable CaMoO₄ crystalline phase. Factors affecting CaMoO₄ combination and glass-in-glass phase separation in calcium borosilicate systems as a function of changing [MoO₃] and [B₂O₃] are examined in this study in order to understand how competition for charge balancers affects phase separation. It further examines the influence of radiation damage on structural modifications using 0.77 to 1.34 GGy of 2.5 MeV electron radiation that replicates inelastic collisions predicted to occur over long-term storage. The resulting microstructure of separated phases and the defect structure were analyzed using electron microscopy, XRD, Raman and EPR spectroscopy prior to and post irradiation. Synthesized calcium borosilicates are observed to form an unusual heterogeneous microstructure composed of three embedded amorphous phases with a solubility limit ~ 2.5 mol% MoO₃. Increasing [B₂O₃] increased the areas of immiscibility and order of (MoO₄)²‾anions, while increasing [MoO₃] increased both the phase separation and crystallization temperature resulting in phases closer to metastable equilibrium, and initiated clustered crystallization for [MoO₃] > 2.5 mol%. β-irradiation was found to have favorable properties in amorphous systems by creating structural disorder and defect assisted ion migration that thus prevented crystallization. It also increased reticulation in the borosilicate network through 6-membered boroxyl ring and Si ring cleavage to form smaller rings and isolated units. This occurred alongside an increased reduction of Mo⁶+ with dose that can be correlated to molybdenum solubility. In compositions with existing CaMoO₄ crystallites, radiation caused a scattering effect, though the crystal content remained unchanged. Therefore β-irradiation can preferentially prevent crystallization in calcium borosilicates for [MoO₃] < 2.5mol%, but has a smaller impact on systems with existing CaMoO₄ crystallites.University of Cambridge, Department of Earth Sciences and EPSRC (Grant No. EP/K007882/1) for an IDS. Cambridge Philosophical Society for a supplementary research grant

β-Irradiation Effects on the Formation and Stability of CaMoO4_{4} in a Soda Lime Borosilicate Glass Ceramic for Nuclear Waste Storage

Molybdenum solubility is a limiting factor to actinide loading in nuclear waste glasses, as it initiates the formation of water-soluble crystalline phases such as alkali molybdates. To increase waste loading efficiency, alternative glass ceramic structures are sought that prove resistant to internal radiation resulting from radioisotope decay. In this study, selective formation of water-durable CaMoO$_{4}$ in a soda lime borosilicate is achieved by introducing up to 10 mol % MoO$_{3}$ in a 1:1 ratio to CaO using a sintering process. The resulting homogeneously dispersed spherical CaMoO$_{4}$ nanocrystallites were analyzed using electron microscopy, X-ray diffraction (XRD), Raman and electron paramagnetic resonance (EPR) spectroscopies prior to and post irradiation, which replicated internal β-irradiation damage on an accelerated scale. Following 0.77 to 1.34 GGy of 2.5 MeV electron radiation CaMoO$_{4}$ does not exhibit amorphization or significant transformation. Nor does irradiation induce glass-in-glass phase separation in the surrounding amorphous matrix, or the precipitation of other molybdates, thus proving that excess molybdenum can be successfully incorporated into a structure that it is resistant to β-irradiation proportional to 1000 years of storage without water-soluble byproducts. The CaMoO$_{4}$ crystallites do however exhibit a nonlinear Scherrer crystallite size pattern with dose, as determined by a Rietveld refinement of XRD patterns and an alteration in crystal quality as deduced by anisotropic peak changes in both XRD and Raman spectroscopy. Radiation-induced modifications in the CaMoO$_{4}$ tetragonal unit cell occurred primarily along the c-axis indicating relaxation of stacked calcium polyhedra. Concurrently, a strong reduction of Mo$^{6+}$ to Mo$^{5+}$ during irradiation is observed by EPR, which is believed to enhance Ca mobility. These combined results are used to hypothesize a crystallite size alteration model based on a combination of relaxation and diffusion-based processes initiated by added energy from β-impingement and second-order structural modifications induced by defect accumulation.Univ. of Cambridge, Dept. of Earth Sciences, and EPSRC (Grant No. EP/K007882/1) for an IDS

Simulation of Eu3+ luminescence spectra of borosilicate glasses by molecular dynamics calculations

Simplified inactive rare-earths doped nuclear waste glasses have been obtained by molecular dynamics (MD) simulation in order to investigate the local structure around the rare-earth by luminescence studies. MD calculations were performed with modified Born–Mayer–Huggins potentials and three body angular terms representing Coulomb and covalent interactions. Atomic positions within the glasses are then determined. Simulations of luminescence spectra were then obtained by calculation of the ligand field parameters affecting each luminescent ion. Considering the C2v symmetry, it is possible to calculate the radiative transition probabilities between the emitter level, 5D0, and the splitted receptor levels, 7FJ (J = 0–3) for each Eu3+ ion. The simulated emission spectra are obtained by convolution of all the Eu3+ ions contributions. A comparison with the experimental data issue from fluorescence line narrowing and microluminescence spectroscopies allowed us not only to validate the simulation of luminescence spectra from simulated environments, but also to confirm the presence and the identification of two major Eu3+ sites distribution in the nuclear glasses thanks to spectra-structure correlations

Helium bubble formation in nuclear glass by in-situ TEM ion implantation

The effect of helium implantation fluences in French nuclear borosilicate glass on He bubble nucleation and growth mechanisms was characterised using in-situ TEM experiments. Observations of implanted glass at 143K indicate that a helium concentration of around 3 at.% is required to nucleate a significant density of nanosized bubbles. He bubble growth is observed for He concentration higher than the estimated number of helium host (> 4 at.%). These results highlight the large capacity of the glassy network for incorporating helium atom

Mono and sequential ion irradiation induced damage formation and damage recovery in oxide glasses: Stopping power dependence of the mechanical properties

Simple and complex borosilicate glasses were irradiated with single and double ion beams of light and heavy ions over a broad fluence and stopping power range. As a result of the heavy ion irradiation (U, Kr, Au), the hardness was observed to diminish and saturate after a decrease by 35 ± 1%. Unlike slow and swift heavy ion irradiation, irradiation with light ions (He,O) induced a saturation hardness decrease of 18 ± 1% only. During double ion beam irradiation; where glasses were first irradiated with a heavy ion (gold) and then by a light ion (helium), the light ion irradiation induced partial damage recovery. As a consequence of the recovery effect, the hardness of the pre-irradiated glasses increased by 10–15% depending on the chemical composition. These results highlight that the nuclear energy loss and high electronic energy loss (≥4 keV/nm) result in significant and similar modifications whereas light ions with low electronic energy loss (≤1 keV/nm) result in only mild damage formation in virgin glasses and recovery in highly pre-damaged glasses. These results are important to understand the damage formation and recovery in actinide bearing minerals and in glasses subjected to self-irradiation by alpha decays. Keyword