CHARACTERIZATION AND THERMAL-HYDRAULIC MODELING OF ENGINEERED BARRIERS FOR A CANADIAN DEEP GEOLOGICAL REPOSITORY FOR USED NUCLEAR FUEL

Within Canada there are more than 2.5 million bundles of spent nuclear fuel with another approximately 2 million bundles to be generated in the future. Canada, and every country around the world that has taken a decision on management of spent nuclear fuel, has decided on long-term containment and isolation of the fuel within a deep geological repository. At depth, a deep geological repository consists of a network of placement rooms where the bundles will be located within a multi-layered system that incorporates engineered and natural barriers. The barriers will be placed in a complex thermal-hydraulic-mechanical-chemical-biological (THMCB) environment. A large database of material properties for all components in the repository are required to construct representative models. Within the repository, the sealing materials will experience elevated temperatures due to the thermal gradient produced by radioactive decay heat from the waste inside the container. Furthermore, high porewater pressure due to the depth of repository along with possibility of elevated salinity of groundwater would cause the bentonite-based materials to be under transient hydraulic conditions. Therefore it is crucial to characterize the sealing materials over a wide range of thermal-hydraulic conditions. A comprehensive experimental program has been conducted to measure properties (mainly focused on thermal properties) of all sealing materials involved in Mark II concept at plausible thermal-hydraulic conditions. The thermal response of Canada’s concept for a deep geological repository has been modelled using experimentally measured thermal properties. Plausible scenarios are defined and the effects of these scenarios are examined on the container surface temperature as well as the surrounding geosphere to assess whether they meet design criteria for the cases studied. The thermal response shows that if all the materials even being at dried condition, repository still performs acceptably as long as sealing materials remain in contact.

Hydro-mechanical characterization of Barmer 1 bentonite from Rajasthan, India

The conceptual model for deep geological disposal of high level nuclear waste (HLW) is based on multiple barrier system consisting of natural and engineered barriers. Buffer/backfill material is regarded as the most important engineered barrier in HLW repositories. Due to large swelling ability, cation adsorption capacity, and low permeability bentonite is considered as suitable buffer material in HLW repositories. Japan has identified Kunigel VI bentonite, South Korea - Kyungju bentonite, China - GMZ bentonite, Belgium - FoCa clay, Sweden - MX-80 bentonite, Spain - FEBEX bentonite and Canada - Avonseal bentonite as candidate bentonite buffer for deep geological repository program. An earlier study on Indian bentonites by one of the authors suggested that bentonite from Barmer district of Rajasthan (termed Barmer 1 bentonite), India is suited for use as buffer material in deep geological repositories. However, the hydro-mechanical properties of the Barmer 1 bentonite are unavailable. This paper characterizes Barmer 1 bentonite for hydro-mechanical properties, such as, swell pressure, saturated permeability, soil water characteristic curve (SWCC) and unconfined compression strength at different dry densities. The properties of Barmer 1 bentonite were compared with bentonite buffers reported in literature and equations for designing swell pressure and saturated permeability coefficient of bentonite buffers were arrived at. (C) 2013 Elsevier B.V. All rights reserved.

Mineralogy of selected geological deposits from the United Kingdom and the Republic of Ireland as possible capping materials for low-level radioactive waste disposal facilities

Solid low-level radioactive waste (LLW) is currently being disposed at a number of facilities in the United Kingdom (UK). The safety of these facilities relies to some extent on the use of engineered barriers, such as a cap, to isolate the waste and protect the environment. Generally, the material used as the barrier layer within such a cap should be of low permeability and it should retain this property over long timescales (beyond a few decades normally required for facilities containing non-radioactive wastes). The objective of this research is to determine the mineralogy of selected geological deposits from the UK and Ireland as part of a larger project to examine their suitability as a capping material, particularly on LLW sites. Mineral transformations, as a result of future climate change, may impact on the long-term performance of the cap and even the disposal facility. X-ray diffraction (XRD) was carried-out on the sand, silt and clay fractions of the London Clay, Belfast Upper Boulder Clay, Irish Glacial Till, Belfast Sleech, and Ampthill Clay geological deposits. Minerals were present that could pose both positive and negative effects on the long-term performance of the cap. Smectite, which has a high shrink swell potential, may produce cracks in London Clay, Belfast Upper Boulder Clay and Ampthill Clay capping material during dry, hotter periods as a possible consequence of future climate change; thus, resulting in higher permeability. Ampthill Clay and Belfast Sleech had elevated amounts of organic matter (OM) at 5.93% and 5.88%, respectively, which may also contribute to cracking. Over time, this OM may decompose and result in increased permeability. Gypsum (CaSO4) in the silt and sand fractions of Ampthill Clay may reduce the impact of erosion during wetter periods if it is incorporated into the upper portion of the cap. There are potential negative effects from the acidity created by the weathering of pyrite (FeS2) present in the silt and sand fractions of Belfast Sleech and Ampthill Clay that could impede the growth of grasses used to stabilize the surface of the capping material if this material is used as part of the vegetative soil layer. Additionally, acidic waters generated from pyrite weathering could negatively impact the lower lying capping layers and the disposal facility in general. However, the calcium carbonate (CaCO3) present in the silt and sand fractions of these deposits, and dolomite (CaMg(CO3)2) in Belfast Sleech, may counter act the acidity.

Tiered approach to corrective action objectives (TACO) : fact sheet series /

"February 1997."

Engineering passive bioreactive barriers: risk-managing the legacy of industrial soil and groundwater pollution

Permeable reactive barriers are a technology that is one decade old, with most full-scale applications based on abiotic mechanisms. Though there is extensive literature on engineered bioreactors, natural biodegradation potential, and in situ remediation, it is only recently that engineered passive bioreactive barrier technology is being considered at the commercial scale to manage contaminated soil and groundwater risks. Recent full-scale studies are providing the scientific confidence in our understanding of coupled microbial (and genetic), hydrogeologic, and geochemical processes in this approach and have highlighted the need to further integrate engineering and science tools.

Electromechanical properties of engineered lead free potassium sodium niobate based materials

K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.