Modelling of long-term diffusion–reaction in a bentonite barrier for radioactive waste confinement

Bentonites have been proposed as buffer material for barriers in geological disposal facilities for radioactive waste. This material is expected to fill up by swelling the void between the canisters containing the waste and the surrounding ground. However, the bentonite barriers may be submitted to changes of humidity, temperature variation, fluid interaction, mass transport, etc. This could modify the physico-chemical performance of the barrier, mainly on the interface with the steel container and with the geological barrier. The engineered barrier development necessitates thus the study of the physico-chemical stability of its mineral component as a function of time under the conditions of the repository in the long-term.The purpose of the present study was two-fold. Firstly, it was hoped to simulate the chemical transformations (geochemical and cation exchange reactions) coupled with diffusion of chemical-elements into the engineered barrier under repository conditions by applying a thermokinetic hydrochemical code (KIRMAT: Kinetic Reactions and Mass transport).Secondly, it was hoped to apply a simplified method to estimate the swelling capacity evolution by a volume balance in the fluid-saturated engineered barrier, considering that the decay of swelling capacity is directly proportional on the volume of transformed montmorillonite and, taking into account that it may be partially compensated by the volume of neo-formed swelling clays.The system modelled herein was considered to consist of 1-m thick zone of water-saturated engineered barrier. This non-equilibrated system was placed in contact with a geological fluid on one side, which was then allowed to diffuse into the barrier, while the other side was kept in contact with a source of metallic iron. Reducing initial conditions(P_O2 0; Eh = − 200 mV) and a constant reaction temperature (100 °C) were considered.The results showed that the EB in contact with the geological fluid was highly transformed after 10,000 years, whereas the most significant chemical processes were illitization, cation exchange and saponization, extending up to 20 cm into the EB. Chemical transformations of minor importance in the EB were identified as well, such as a neo-formation of silicates (quartz, cristobalite), anhydrite, laumontite, magnetite and chlorite in the system.A simplified method based on volume balance showed that the swelling capacity of the bentonite barrier is slightly affected after 10,000 years of diffusion–reaction (D close to 1) because the volume of neo-formed swelling-clays is almost directly proportional to the volume of transformed Na/Ca-montmorillonite, except for a strong illitization and/or neo-formation of non-swelling clays. In the present study, this simple approach predicted that the decay of swelling capacity of the engineered barrier is drastically affected close to the geological barrier-engineered barrier interface. Out this zone the swelling capacity decay lies between 5% and 11%.     

On‐line mixing during injection and simultaneous curing in liquid composite molding processes

Liquid composite molding (LCM) processes such as resin transfer molding (RTM) and vacuum assisted RTM (VARTM) are used to manufacture high quality and net‐shape fiber reinforced composite parts. All LCM processes impregnate fiber preforms packed in a mold cavity with a thermoset resin. After the preform is fully saturated, the injection is discontinued but the resin continues to cure. Once the curing step is complete, the part is de‐molded. The resin has to be mixed with a curing agent to cure. Typically, the resin and the curing agent are mixed together in a pressure pot before the injection. This has several disadvantages, such as storage of large amounts of hazardous polymerizing resin, wastage, and cleaning of cured resin from the injection line. This paper proposes the implementation and calibration of an alternative to this technique. The approach is to mix the curing agent with the resin as the resin enters the mold through a separate system featuring two feed‐lines. Such a system will enable one to maintain a uniform gel time throughout the part by varying the mixing ratio of resin and the catalyst during the injection. An experimental study of such on‐line mixing to obtain simultaneous curing and to reduce the overall curing time is conducted and presented in this paper. Implementation of a control scheme that varies the curing agent during injection and its effect on cure time is benchmarked with the process in which the percentage of curing agent is held constant. The gel time for the fabricated parts was reduced by 20–25% by continuously varying the percentage of curing agent during injection. POLYM. COMPOS., 26:74–83, 2005. © 2004 Society of Plastics Engineers     

A Striking Parallel Between Cardiolipin Fatty Acid Composition and Phylogenetic Belonging in Marine Bivalves: A Possible Adaptative Evolution?

Thirty-five species of marine mollusk bivalves were analyzed for their fatty acid (FA) composition of cardiolipin (Ptd(2)Gro). All species showed a Ptd(2)Gro with strong selectivity for only a few polyunsaturated fatty acids, but three characteristic FA profiles emerged, with clear parallels to bivalve phylogeny. A first group of 12 species belonging to the Eupteriomorphia subgroup (Filibranchia) was characterized by a Ptd(2)Gro almost exclusively composed of 22:6n-3, whereas in the four Filibranchia Pteriomorph species analyzed, this FA was combined with substantial proportions of 18:2n-6 and 18:3n-3. Finally, a third group of 20 species, all belonging to the Heterodonta subclass, possessed Ptd(2)Gro containing predominantly both 22:6n-3 and 20:5n-3. Polyunsaturated FA moieties and arrangements in the Ptd(2)Gro of some marine species investigated in other classes of the mollusk phylum (Gastropoda, Polyplacophora) were found to be different. The present results suggest that the specific Ptd(2)Gro FA compositions in bivalves are likely to be controlled and conserved in species of the same phylogenetic group. Functional significances of the evolution of this mitochondrial lipid structure in bivalves are discussed.     

Influence of epitaxial stress on spinodal decomposition in binary alloys with large size effects: application to the Au–Ni system

Within the framework of Cahn’s pioneering theory of spinodal decomposition, the effect of the epitaxial stress on the stability of a binary alloy solid solution against infinitesimal compositional fluctuations is revisited. It is shown that the elastic energy term due to a coherent lattice mismatch with a substrate modifies the linearised diffusion equation. This term is particularly high when size effects between the two constituents are strong. It is then necessary to take into account anharmonic terms in the expression of the elastic energy. From the modified diffusion equation, a new spinodal curve, called the epitaxial coherent spinodal, may be calculated for different substrate lattice parameters. The results of the model are compared with recent experiments on coherently grown (001) Au–Ni alloys. A modulated structure has been evidenced upon annealing which is in good agreement with our calculations.

Résumé

Dans le cadre de la théorie de la décomposition spinodale développèe par Cahn, nous présentons l’effet des contraintes épitaxiales sur la stabilitéd’une solution solide d’alliage binaire soumise ádes fluctuations de compostion infinitésimales. Les contraintes induites par l’épitaxie cohérente sur un substrat ayant un paramètre de maille différent de celui de la solution solide considérée sont àl’origine d’un terme d’énergie élastique dont il faut tenir compte dans l’équation de diffusion. Ce terme devient particulièrement important lorsque les effets de taille entre les deux constituants sont grands. Nous montrons qu’il est alors nécessaire de considérer dans l’expression de l’énergie élastique les termes anharmoniques. Une nouvelle spinodale, appelée spinodale cohérente épitaxiale, peut être calculée pour différentes valeurs du paramètre de maille du substrat. Les calculs sont comparés avec les résulats expérimentaux obtenus sur des alliages Au–Ni (001) élaborés de manière cohérente. Une structure modulée a étémise en evidence au cours de recuits, ce qui est en accord avec les résultats du modèle.     

Interface step-induced thin-film delamination and buckling

Atomistic simulations based on experimental observations provide the first evidence that the interface delamination of a thin film from its substrate may start from interface steps. Buckling of the film after interface gliding from both edges of its delaminated part is also observed. In the framework of the Föppl–von Kármán theory of thin plates, the expression of the critical strain beyond which the film buckles has been then analytically determined as a function of the step height and gliding displacements. Both numerical and analytical results confirm that the formation of blisters is favoured in the neighbourhood of interfacial imperfections.     

Volatilization and Transport Mechanisms During Cr Oxidation at 300 °C Studied In Situ by ToF-SIMS

The oxidation of chromium at 300 °C was investigated in situ by ToF-SIMS for three different oxygen pressures (\(P_{{{\text{O}}_{2} }} = 2.0 \times 10^{ - 7}\), 6.0 × 10^?7 and 2.0 × 10^?6 mbar). Sequential exposure to the ¹⁸O isotopic tracer was performed to reveal the governing transport mechanism in the oxide film. The evolution of the oxide thickness was monitored. Volatilization of Cr₂O₃ was evidenced. A model was used to describe the kinetics resulting from the measurements. Both the parabolic and volatilization constants showed a dependence on oxygen partial pressure like \(P_{{{\text{O}}_{2} }}^{ - 1/n}\), with n = 1.9 ± 0.1, indicating a defect structure mainly consisting of oxygen vacancies. The re-oxidation in ¹⁸O₂ shows a growth of the oxide layer at the metal/oxide interface, demonstrating an oxidation process governed by anionic transport via oxygen vacancies. The diffusion coefficient of oxygen in the oxide was determined by fitting the ToF-SIMS depth profiles. It is 2.0 × 10^?18 cm² s^?1.     

Thermal stability of NO 2 ⋅ and NO⋅ radicals formed in an Al23 catalyst during its preparation from a nitrate precursor

During the preparation of alumina as a catalyst support from aluminium nitrates by precipitation with a NH₄OH base, NO ₂ ^⋅ radicals have been formed in the catalyst after calcination under air in the solid at different temperatures. These radicals remained stable until a calcination temperature of 800°C. When the calcined catalyst was degassed under vacuum above 300 °C, the NO ₂ ^⋅ was reduced to give NO^⋅ and O^- species which were both tightly trapped in the solid. These latter species remained stable until vacuum treatment at 800 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nuclear Magnetic Resonance of Physisorbed 129Xe Used as a Probe to Investigate Porous Solids

Xenon is an inert gas with a large electronic environment that makes it sensitive to any interaction, even physical. In the case of ¹²⁹Xe isotope (spin 1/2), the resulting electronic perturbation is directly transmitted to the nucleus and, therefore, affects the nuclear magnetic resonance chemical shift. In this review, we report exhaustively up to 1996 the many applications of this technique in both fundamental and applied research in the fields of microporous and mesoporous solids.