[en] The development of glass materials for long-term storage of high-level waste implies determining the glass thermal stability and notably assessing the risk of devitrification. Previous studies of the French nuclear waste glass have identified the crystalline phases and the domains in which they form, and have shown that devitrification is minimal. Modeling the long-term crystallization behavior requires an investigation of the thermodynamic and kinetic mechanisms liable to induce crystallization during cooling. The first step in this approach is to determine the nucleation and growth curves for each of the component phases. Crystals including CaMoO₄, CeO₂ and ZnCr₂O₄ were identified in glasses heat-treated at temperatures between 630 C and 1,110 C, and the time and thermal dependence of the CaMoO₄ morphology were evaluated. The nucleation and growth kinetics of these phases were determined by optical microscopy and SEM, and the impact of impurities was addressed by studying two glasses, with and without platinoid elements. The results indicated enhanced nucleation kinetics in glass containing platinoid elements. No induction time was observed before permanent nucleation in either of the glasses, and rapid saturation of nucleation kinetics--synonymous with the depletion of active centers of nucleation--was detected after a few hours. Furthermore, similar growth kinetics were observed in both glasses. The nucleation and growth curves coincided for all the phases. Peak values were much higher for nucleation than for growth kinetics, confirming the need for thorough investigation of the mechanisms occurring in and below the glass transition range, i.e., in the non-equilibrium state

[en] Nine samples of the 'R7T7' glass composition selected to vitrify fission product solutions in France were prepared with added platinoid elements (ruthenium, rhodium and palladium) in soluble form and as insoluble metal particles in solution, and their major properties were measured. Regardless of the initial form when added to the glass the platinoids always formed the same heterogeneous inclusions in the final glass: RuO₂ precipitates which were often found as aggregates, and polymetallic (Pd, Rh and Te) inclusions. The particles tended to settle in the molten glass. The viscosity increased by about 20% at 1100 deg C. The mechanical properties and short-term leach rates were not significantly affected. Crystallization increased by a factor of 2 or 3 in heat-treated glass specimens but did not exceed a few volume percent. However, as the short-term leach rate did not significantly increase, the glass properties were very satisfactory

[en] The fission products resulting from reprocessing of commercial spent fuel are currently vitrified industrially by COGEMA at La Hague. The properties of 21 non-radioactive borosilicate glass samples containing between 4 and 6% of the platinum-group metals (PGM: Pd and Ru) compared with 1.6% in the industrial glass were investigated for chemical composition variations covering the full specification range. After a brief morphological description of the undissolved PGM in the glass, the viscosity variations at temperatures ranging from 1100 to 1200 deg C are discussed with emphasis on the effects of the particle inclusions on the rheological properties of the glass. Variations in the chemical durability of quenched glass specimens are then discussed. The initial leach rate V₀ at 100 deg C remained near the values obtained for the reference glass. The same tests were repeated on glass heat-treated to obtain maximum crystallization, and the results confirmed that the chemical durability of the glass is practically unaffected by the crystallization observed in this type of glass. Copyright (2001) Material Research Society

[en] The vitrification of high-level waste is the internationally recognized standard to minimize the impact to the environment resulting from waste disposal as well as to minimize the volume of conditioned waste to be disposed of. COGEMA has been vitrifying high-level waste industrially for over 20 years and is currently operating three commercial vitrification facilities based on a hot metal crucible technology, with outstanding records of safety, reliability and product quality. To further increase the performance of vitrification facilities, CEA and COGEMA have been developing the cold crucible melter technology since the beginning of the 1980s. This type of melter is characterized by a virtually unlimited equipment service life and a great flexibility in dealing with various types of waste and allowing development of high temperature matrices. In complement of and in parallel with the vitrification process, a glass formulation methodology has been developed by the CEA in order to tailor matrices for the wastes to be conditioned while providing the best adaptation to the processing technology. The development of a glass formulation is a trade-off between material properties and qualities, technical feasibility, and disposal safety criteria. It involves non-radioactive and radioactive laboratories in order to achieve a comprehensive matrix qualification. Several glasses and glass ceramics have thus been studied by the CEA to be compliant with industrial needs and waste characteristics: glasses or other matrices for a large spectrum of fission products, or for high contents of specifics elements such as sodium, phosphate, iron, molybdenum, or actinides. New glasses or glass-ceramics designed to minimize the final wasteform volume for solutions produced during the reprocessing of high burnup fuels or to treat legacy wastes are now under development and take benefit from the latest CEA hot-laboratories and technology development. The paper presents the CEA state-of-the-art in developing matrices or glasses and provides several examples

[en] Models have been developed to calculate the density, molten-state viscosity and initial corrosion rate according to the chemical composition of glass formulations used to vitrify high-level fission product solutions from reprocessed light water reactor fuel. Developed from other published work, these models have been adapted to allow for the effects of platinoid (Ru, Pd, Rh) inclusions on the molten glass rheology. (authors). 15 refs., 10 figs., 1 tab

[en] Studies have been conducted in France to minimize the potential long-term impact of nuclear waste by enhanced chemical separation of the minor actinides (Np, Am, Cm) and some long-lived fission products (I, Cs, Tc). Two options may be considered following this work: (i) the initial reference option is transmutation by neutron bombardment in nuclear facilities, (ii) the second option would be to incorporate the separated elements into an inorganic matrix ensuring long-term stability. In the case of specific conditioning, zirconolite and hollandite are the potential host phases for the minor actinides and caesium, respectively. Both of these matrices have shown strong potential: (i) for incorporating the respective radioelement in the crystalline structure, (ii) for fabricating the ceramic by natural sintering in air, (iii) for chemical durability with a very low initial alteration rate (about 10^-2 g m^-2 d^-1 at 100 C), then very rapidly reach alteration rates more than four orders of magnitude lower. In the case of zirconolite ceramics, the high chemical durability is conserved even after amorphization of the crystalline structure by external irradiation with heavy ions or by self-irradiation in natural zirconolites 550 million years old. (authors)

[en] Zirconolite-based (nominally CaZrTi₂O₇) glass-ceramics belonging to the SiO₂Al₂O₃-CaO- ZrO₃-TiO₂ system are good waste forms for the specific immobilisation of actinides. The understanding of their crystallisation processes implies to investigate the structure of the glass. Thus, the environment around Ti, Zr (nucleating agents) and Nd (trivalent actinides surrogate) was characterised in parent glasses. Electron spin resonance (ESR) study of the small amount of Ti³⁺ occurring in the glass enabled to identify two types of sites for titanium: the main one is of C_4v or D_4h symmetry. EXAFS showed that Zr occupied a quite well defined 6-7-fold coordinated site with second neighbours which could correspond to Ca/Ti and Zr. Nd environment was probed by optical spectroscopies (absorption, fluorescence), ESR and EXAFS. All these techniques demonstrated that the environment around Nd was very constrained by the glassy network. Notably, Nd occupies a highly distorted 8-9-fold coordinated site in the parent glass. (authors)

[en] Models have been developed to calculate the density, molten-state viscosity and initial corrosion rate according to the chemical composition of glass formulations used to vitrify high-level fission product solutions from reprocessed light water reactor fuel. Developed from other published work, these models have been adapted to allow for the effects of platinoid (Ru, Pd, Rh) inclusions on the molten glass rheology

[en] New nuclear glass compositions, able to immobilize highly active liquid wastes arising from high burn-up UO₂ fuel reprocessing, are being studied. Investigations are being performed on rare earth rich glasses, known as durable matrices. After a preliminary study, a basic glass composition was selected (Glass A, wt. %): 51.0 SiO₂ - 8.5 B₂O₃ - 12.2 Na₂O - 4.3 Al₂O₃ - 4.8 CaO - 3.2 ZrO₂ - 16.0 Nd₂O₃. The aim of this study is to determine the local environment of the rare earth in this glass and its evolution according to neodymium. To achieve this objective, glasses were prepared from the baseline Glass A with variable neodymium oxide amounts (from 0 to 30 wt. % Nd₂O₃). By coupling characterization methods such as EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, ¹¹B, ²⁷Al MAS-NMR and Raman spectroscopy, pieces of information the rare earth surroundings in the glass were obtained. (authors)

[en] The NMC program (scientific feasibility (year 2001) and technical feasibility (year 2006)) is presented. Researches are carried out on the following matrices: zirconolite based materials, glasses, hollandite based materials, apatites and thorium phosphate diphosphate. The aim is to give at the latest in the year 2006 a comparison of the different matrices in order to make a choice. The comparison is based on 1)the knowledge on the material (structure, % of radionuclide in the structure, phase diagram..) 2)the physical properties (mechanical properties, thermal conductivity..) 3)the irradiation resistance (amorphization dose, annealing process, change in properties..) 4)the long-term leaching behavior on non radioactive and radioactive samples 5)the process: (melting or sintering temperature, number of steps, secondary wastes..)