[en] The starting point for this report is the discrepancy reported in previous work between the reaction-diffusion calculations and the CEX-1 experiment, which involves storage of defected fuel elements in air at 150 deg C. This discrepancy is considerably diminished here by a more critical choice of theoretical parameters, and by taking into account the fact that different CEX-1 fuel elements were oxidized at very different rates and that the fuel element used previously for comparison with theoretical calculations actually underwent two limited-oxygen-supply cycles. Much better agreement is obtained here between the theory and the third, unlimited-air, storage period of the CEX-1 experiment. The approximate integral method is used extensively for the solution of the one-dimensional diffusion moving-boundary problems that may describe various storage periods of the CEX-1 experiment. In some cases it is easy to extend this method to arbitrary precision by using higher moments of the diffusion equation. Using this method, the validity of quasi-steady-state approximation is verified. Diffusion-controlled oxidation is also studied. In this case, for the unlimited oxygen supply, the integral method leads to an exact analytical solution for linear geometry, and to a good analytical approximation of the solution for the spherically symmetric geometry. These solutions may have some application in the analysis of experiments on the oxidation of small UO₂ fragments or powders when the individual UO₂ grains may be considered to be approximately spherical. (author). 23 refs., 5 tabs., 11 figs

[en] The effects of variations in geosphere conditions and of the properties of the backfill material on the performance of the engineered barriers have been examined using a numerical Cu container failure model. The thickness of the exclusion zone between the vault and the nearest major water-bearing fracture has been varied between 1 and 50 m. The groundwater [O₂] has been varied between limits of 1 and 7360 ng·g^-1, the latter value being equivalent to the hypothetical situation of aerated saline groundwater at the ambient rock temperature of 17 degrees C. The properties of the excavation-disturbed zone (EDZ) have been varied to simulate both blast-induced and stress-induced damage. Finally, the effect of the particle size of crushed granite, of reduced heat output from the container and the effect of substituting pyrite for biotite on the performance of the backfill material has been determined. The impact of these variables on the corrosion rate, the extent of the four O₂-consumption reactions and the fate of FE(II) dissolved from the biotite (or pyrite) in the backfill and EDZ has been examined. The results of the various simulations suggest that the engineered barriers (the container and the buffer and backfill materials) can isolate the fuel almost indefinitely, regardless of the geosphere conditions. Copper containers are predicted not to fail by corrosion within the analysis period of ∼10⁵ a. The robustness of the engineered barriers is a result of (i) the low rates of mass transport in saturated buffer and backfill materials and (ii) the presence of an excess of redox-buffering FE(II) minerals in the backfill. (author)

[en] In this report we develop response functions for the mass transport of radionuclides from a small pinhole-sized defect in a waste container located in a cylindrical disposal room. The disposal rooms are considered to be Idled with buffer and backfill materials composed of mixtures of clay and sand or crushed rock. Mass transport of radionuclides released gradually into the room by diffusion through a pinhole can be determined by convolution with the response functions. A model based on the boundary-integral method (BIM) is described here. In this model the room is represented by three coaxial cylinders comprised of buffer, backfill and excavation damage zone, surrounded by the sparsely fractured rock. The main result of the model is the flux integrated over the surface of the excavation damage zone which can serve as the input into a model representing the surrounding geosphere. The integrated flux obtained from the BIM model is compared with the integrated flux obtained from the finite-element code called MOTIF (Chan et al. 1987). The finite-element model consists of coaxial rectangular regions that have the same volume as the respective cylinders in the BIM model. Sample numerical calculations are shown for ¹²⁹I which is one of longest lived and most readily Teachable radionuclides that would be released from a failed container. The two models give identical results in the absence of groundwater flow, and almost identical results for a range of small groundwater velocities. For very large groundwater velocities the BIM model is conservative (it gives higher integrated fluxes than the MOTIF model), except when the source is near the end of the room towards which the flow is directed. (author)

[en] A mechanistic model has been developed to predict the long-term corrosion behaviour of copper nuclear fuel waste containers in a Canadian disposal vault. The model is based on a detailed description of the electrochemical, chemical, adsorption and mass-transport processes involved in the uniform corrosion of copper, developed from the results of an extensive experimental program. Predictions from the model are compared with the results of some of these experiments and with observations from a bronze cannon submerged in seawater saturated clay sediments. Quantitative comparisons are made between the observed and predicted corrosion potential, corrosion rate and copper concentration profiles adjacent to the corroding surface, as a way of validating the long-term model predictions. (author)

[en] The buffer material surrounding the containers in a Canadian nuclear fuel waste disposal vault will partially desiccate as a result of the elevated temperature at the container surface. This will lead to a period of corrosion in a moist air atmosphere. Corrosion will either take the form of slow oxidation if the container surface remains dry or aqueous electrochemical corrosion if the surface is wetted by a thin liquid film. The relevant literature is reviewed, from which it is concluded that corrosion should be uniform in nature, except if the surface is wetted, in which case localized corrosion is a possibility. A quantitative analysis of the extent and rate of uniform corrosion during the unsaturated period is presented. Two bounding cases are considered: first, the case of slow oxidation in moist air following either logarithmic or parabolic oxide-growth kinetics and, second, the case of electrochemically based corrosion occurring in a thin liquid film uninhibited by the growth of corrosion products. (author)

[en] A model is described that predicts the rate of O₂ consumption in a sealed nuclear fuel waste disposal vault as a result of container corrosion, reaction with biotite and the oxidation of organics and other oxidizable impurities in the clay. The most important reactions leading to the consumption of O₂ for Cu containers in a conceptual Canadian disposal vault are container corrosion, the oxidation of dissolved Cu(l) and the oxidation of organics and other impurities in the clay. Consumption of O₂ by the oxidation of dissolved Fe(Il) from biotite is significant in backfill materials containing crushed granite and in the rock itself. The O₂ initially trapped in the disposal vault is predicted to be consumed in between 50 and 670 a. (author)

[en] Porous and semi-permeable layers play a role in many corrosion processes. Porous layers may simply affect the rate of corrosion by affecting the rate of mass transport of reactants and products to and from the corroding surface. Semi-permeable layers can further affect the corrosion process by reacting with products and/or reactants. Reactions in semi-permeable layers include redox processes involving electron transfer, adsorption, ion-exchange and complexation reactions and precipitation/dissolution processes. Examples of porous and semi-permeable layers include non-reactive salt films, precipitate layers consisting of redox-active species in multiple oxidation states (e.g., Fe oxide films), clay and soil layers and biofilms. Examples of these various types of processes will be discussed and modelling techniques developed from studies for the disposal of high-level nuclear waste presented. (author). 48 refs., 1 tab., 12 figs

[en] An electrochemically based model for predicting the effects of α-radiolysis, the precipitation of U(VI) corrosion products and redox processes with Fe and Fe(II) on the dissolution of UO₂ is described. Various aspects of the model are presented, including: the underlying mechanism, the reaction-diffusion equations used to describe the mass transport and homogeneous reactions of the various species considered in the model, the geometrical grid used to simulate both experimental and used fuel/container geometries and the electrochemical boundary conditions used for the numerical solution of the reaction-diffusion equations. The results of preliminary simulations are also discussed

[en] The incorporation of atomic pseudopotentials in the calculation of the electronic structure of molecules and larger complexes leads to a decrease in the size of the problem since in the frozen core approximation only valence electrons need to be considered. PSEPOT is a subprogram that computes matrix elements of atomic pseudopotentials occuring in the above mentioned calculations provided that both the pseudopotentials and the basis functions are expressed as linear combinations of different Gaussians. (orig.)

[en] The assumptions upon which the lifetime failure model used in the postclosure assessment is based are reevaluated. In particular, the conservations involved in assuming that crevice initiation would occur, and that sufficient oxygen would be present to maintain crevice propagation to failure, are discussed. Unless the period required to saturate the environment around the container can be specified with some certainty, it remains necessary to assume corrosion would initiate rapidly on all containers. A modified version of the container lifetime model has been developed which avoids the need to use averaged temperature profiles. In this model, these profiles are converted to propagation rate profiles using an experimental activation energy and then numerically integrated to predict container failure times. A damage function is developed relating the maximum depth of penetration by crevice corrosion to either the time since emplacement in the vault or the total amount of oxygen consumed. This function is used to estimate the maximum penetration depth expected if all the oxygen available in a borehole is consumed in crevice corrosion and to determine the impact on container lifetimes of various repassivation criteria. The factors likely to cause repassivation are summarized, and a number of engineering approaches to extending container lifetimes suggested. (author). 22 refs., 1 tab., 17 figs