Optimising sodium incorporation into potassium-activated metakaolin-based alkali-activated materials

Chaerun, R. I.; Sato, Junya; Hiraki, Yoshihisa; Yoshida, Yukihiko; Sato, Tsutomu*; Osugi, Takeshi

Construction and Building Materials, 500, p.144270_1 - 144270_10, 2025/11

https://doi.org/10.1016/j.conbuildmat.2025.144270

Alkali-activated materials (AAMs), particularly those derived from metakaolin, have gained significant attention as sustainable binders for hazardous waste immobilisation, owing to their dense microstructure and chemical durability. Their amorphous aluminosilicate framework enables effective encapsulation of hazardous materials and reduces environmental risks. However, maintaining the stability of this amorphous network is challenging, particularly when sodium (Na)-rich precursors are used, as excess Na) promotes crystallisation and compromises matrix integrity. This study systematically investigates the influence of Na) concentration on the structural stability of metakaolin-based AAMs activated primarily with potassium (K)). The objective is to identify the threshold Na incorporation level that preserves the amorphous structure and maintains chemical stability. Transmission electron microscopy (TEM), Raman spectroscopy, and thermodynamic modelling were employed to examine the structural evolution of K-AAMs across a range of Na:K molar ratios. The results reveal that higher Na:K ratios induce nanopore formation and early crystallisation of Na-rich zeolitic phases, which can reduce matrix stability. In contrast, an optimal Na:K ratio was identified that maintains the amorphous network and preserves the aluminosilicate framework. These findings provide valuable insights into optimising K-AAMs for advanced, durable waste encapsulation technologies.

Evolution of radionuclide transport and retardation processes in uplifting granitic rocks, Part 2; Modelling coupled processes in uplift scenarios

Metcalfe, R.*; Benbow, S. J.*; Kawama, Daisuke*; Tachi, Yukio

Science of the Total Environment, 958, p.177690_1 - 177690_17, 2025/01

https://doi.org/10.1016/j.scitotenv.2024.177690

Uplifting fractured granitic rocks occur in substantial areas of countries such as Japan. A repository site would be selected in such an area only if it is possible to make a safety case, accounting for the changing conditions during uplift. The safety case must include robust arguments that chemical processes in the rocks around the repository will contribute sufficiently to minimise radiological doses to biosphere receptors. To provide confidence in the safety arguments, numerical models need to be sufficiently realistic, but also parameterised conservatively (pessimistically). However, model development is challenging because uplift involves many complex couplings between groundwater flow, chemical reactions between water and rock, and changing rock properties. The couplings would affect radionuclide mobilisation and retardation, by influencing diffusive radionuclide fluxes between groundwater flowing in fractures and effectively immobile porewater in the rock matrix and radionuclide partitioning between water and solid phases, via: (i) mineral precipitation/dissolution; (ii) mineral alteration; and (iii) sorption/desorption. It is difficult to represent all this complexity in numerical models while showing that they are parameterised conservatively. Here we present a modelling approach, illustrated by simulation cases for some exemplar radioelements, to identify realistically conservative process conceptualisations and model parameterisations.

Modelling of the LTDE-SD radionuclide diffusion experiment in crystalline rock at the sp Hard Rock Laboratory (Sweden)

Soler, J. M.*; Meng, S.*; Moreno, L.*; Neretnieks, I.*; Liu, L.*; Keklinen, P.*; Hokr, M.*; ha, J.*; Vetenk, A.*; Reimitz, D.*; et al.

Geologica Acta, 20(7), 32 Pages, 2022/07

https://doi.org/10.1344/GeologicaActa2022.20.7

Task 9B of the SKB Task Force on Modelling of Groundwater Flow and Transport of Solutes in fractured rock focused on the modelling of experimental results from the LTDE-SD in situ tracer test performed at the sp Hard Rock Laboratory in Sweden. Ten different modelling teams provided results for this exercise, using different concepts and codes. Three main types of modelling approaches were used: (1) analytical solutions to the transport-retention equations, (2) continuum-porous-medium numerical models, and (3) microstructure-based models accounting for small-scale heterogeneity (i.e. mineral grains and microfracture distributions). The modelling by the different teams allowed the comparison of many different model concepts, especially in terms of potential zonations of rock properties (porosity, diffusion, sorption), such as the presence of a disturbed zone at the rock and fracture surface, the potential effects of micro- and cm-scale fractures.

Predictive modeling of a simple field matrix diffusion experiment addressing radionuclide transport in fractured rock. Is it so straightforward?

Soler, J. M.*; Neretnieks, I.*; Moreno, L.*; Liu, L.*; Meng, S.*; Svensson, U.*; Iraola, A.*; Ebrahimi, K.*; Trinchero, P.*; Molinero, J.*; et al.

Nuclear Technology, 208(6), p.1059 - 1073, 2022/06

https://doi.org/10.1080/00295450.2021.1988822

The SKB Task Force is an international forum on modelling of groundwater flow and solute transport in fractured rock. The WPDE experiments are matrix diffusion experiments in gneiss performed at the ONKALO underground facility in Finland. Synthetic groundwater containing several conservative and sorbing tracers was injected along a borehole interval. The objective of Task 9A was the predictive modelling of the tracer breakthrough curves from the WPDE experiments. Several teams, using different modelling approaches and codes, participated in this exercise. An important conclusion from this exercise is that the modelling results were very sensitive to the magnitude of dispersion in the borehole opening, which is related to the flow of water. Focusing on the tails of the breakthrough curves, which are more directly related to matrix diffusion and sorption, the results from the different teams were more comparable.

Modelling concrete degradation by coupled non-linear processes

Oda, Chie; Kawama, Daisuke*; Shimizu, Hiroyuki*; Benbow, S. J.*; Hirano, Fumio; Takayama, Yusuke; Takase, Hiroyasu*; Mihara, Morihiro; Honda, Akira

Journal of Advanced Concrete Technology, 19(10), p.1075 - 1087, 2021/10

https://doi.org/10.3151/jact.19.1075

Concrete in a transuranic (TRU) waste repository is considered a suitable material to ensure safety, provide structural integrity and retard radionuclide migration after the waste containers fail. In the current study, coupling between chemical, mass-transport and mechanical, so-called non-linear processes that control concrete degradation and crack development were investigated by coupled numerical models. Application of such coupled numerical models allows identification of the dominant non-linear processes that will control long-term concrete degradation and crack development in a TRU waste repository.

Evolution of the reaction and alteration of mudstone with ordinary Portland cement leachates; Sequential flow experiments and reactive-transport modelling

Bateman, K.; Murayama, Shota*; Hanamachi, Yuji*; Wilson, J.*; Seta, Takamasa*; Amano, Yuki; Kubota, Mitsuru*; Ouchi, Yuji*; Tachi, Yukio

Minerals (Internet), 11(9), p.1026_1 - 1026_23, 2021/09

https://doi.org/10.3390/min11091026

Using natural systems evidence to test models of transformation of montmorillonite

Savage, D.*; Wilson, J.*; Benbow, S.*; Sasamoto, Hiroshi; Oda, Chie; Walker, C.*; Kawama, Daisuke*; Tachi, Yukio

Applied Clay Science, 195, p.105741_1 - 105741_11, 2020/09

https://doi.org/10.1016/j.clay.2020.105741

Safety functions for the clay buffer in a repository for high-level radioactive waste (HLW) are fulfilled if the presence of montmorillonite with high swelling capacity and low permeability is maintained in the long-term. The transformation of montmorillonite to the non-swelling mineral likely illite is addressed in most safety assessments by using simple semi-empirical kinetic models, but this approach contrasts with more complex reactive-transport simulations. In the present study, reactive-transport simulations are compared with simple semi-empirical kinetic models. Results suggest that reactive-transport simulations err on the side of conservatism, but may produce unrealistic estimates of illitization. This comparison demonstrates that reactive-transport models may be carefully applied to simulate the long-term evolution of near field environment for HLW disposal.

Evaluation and modelling report of Task 9A based on comparisons and analyses of predictive modelling results for the REPRO WPDE experiments; Task 9 of SKB Task Force GWFTS - Increasing the realism in solute transport modelling based on the field experiments REPRO and LTDE-SD

Soler, J. M.*; Neretnieks, I.*; Moreno, L.*; Liu, L.*; Meng, S.*; Svensson, U.*; Trinchero, P.*; Iraola, A.*; Ebrahimi, H.*; Molinero, J.*; et al.

SKB R-17-10, 153 Pages, 2019/01

The SKB Task Force is an international forum on modeling of groundwater flow and solute transport in fractured rock. The WPDE experiments are matrix diffusion experiments in gneiss performed at the ONKALO underground facility in Finland. Synthetic groundwater containing several conservative and sorbing tracers was injected along a borehole interval. The objective of Task 9A was the predictive modeling of the tracer breakthrough curves from the WPDE experiments. Several teams, using different modelling approaches, participated in this exercise. An important conclusion from this exercise is that the modeling results were very sensitive to the magnitude of dispersion in the borehole opening, which is related to the flow of water. Focusing on the tails of the breakthrough curves, which are more directly related to matrix diffusion and sorption, the results from the different teams were more comparable. The modeling results have also been finally compared to the measured breakthroughs.

OECD/NEA benchmark on pellet-clad mechanical interaction modelling with fuel performance codes; Impact of number of radial pellet cracks and pellet-clad friction coefficient

Dostl, M.*; Rossiter, G.*; Dethioux, A.*; Zhang, J.*; Amaya, Masaki; Rozzia, D.*; Williamson, R.*; Kozlowski, T.*; Hill, I.*; Martin, J.-F.*

Proceedings of Annual Topical Meeting on Reactor Fuel Performance (TopFuel 2018) (Internet), 10 Pages, 2018/10

A Modelling study on water radiolysis for primary coolant in PWR

Mukai, Satoru*; Umehara, Ryuji*; Hanawa, Satoshi; Kasahara, Shigeki; Nishiyama, Yutaka

Proceedings of 20th International Conference on Water Chemistry of Nuclear Reactor Systems (NPC 2016) (USB Flash Drive), 9 Pages, 2016/10

In Japanese PWR, the concentration of dissolved hydrogen in the primary coolant is controlled in the range from 25 cc/kg-HO to 35 cc/kg-HO for suppression of water decomposition. However this concentration is desired to reduce for the purpose of radiation source reduction in Japan. So, the concentration due to water radiolysis in primary coolant was evaluated at lower hydrogen concentration by the water radiolysis model in consideration of ray, fast neutron and alpha ray due to the reaction B(n,)Li. The results of evaluation showed that the water radiolysis was suppressed even if the hydrogen concentration was decreased to 5 cc/kg-HO. The effects of the different G-value and the rate constants of major reaction on the concentration of HO and O were studied under hydrogen addition. We also focused on the effect of the alpha radiolysis in boron acid water.