Influence of superplasticizers on the long-term properties of cement pastes and possible impact on radionuclide uptake in a cement-based repository for radioactive waste

Abstract Cementitious materials will be used for the construction of the engineered barrier of the planned repositories for radioactive waste in Switzerland. Superplasticizers (SPs) are commonly used to improve the workability of concretes and, along with a set accelerator (Acc), to produce shotcrete. In this study the influence of a polycarboxylate- (PCE) and a polynaphthalene-sulphonate-based (PNS) SP on the hydration process, mineral composition and the sorption behaviour of metal cations has been investigated using an ordinary Portland cement (OPC), a low-alkali cement mix (LAC) consisting of CEM III-type cement and nanosilica, and a shotcrete-type cement mix (ESDRED) consisting of a CEM I-type cement and silica fume prepared in the presence of an alkali-free set accelerator. Both the PCE and PNS SP do not significantly influence the amount and quantity of hydrates formed during hydration. The concentration of both SPs decreased rapidly in the early stage of the hydration process for all cements due to sorption onto cement phases. After 28 days of hydration and longer, the concentration of the PNS SP in the pore fluids of all cements was generally lower than that of the PCE SP, indicating stronger uptake of the PNS SP. The formate present in the Acc sorbs only weakly onto the cement phases, which led to higher aqueous concentration of organics in the ESDRED cement than in OPC and LAC. Sorption experiments with 63 Ni, 152 Eu and 228 Th on a cation exchange resin indicate that, at concentrations above 0.1 g L −1 , the two SPs could reduce sorption of metal cations. Thermodynamic modelling further indicates that radionuclide complexation by formate at the concentration level in Acc can be excluded, suggesting that the apparent effect of Acc in the sorption measurements on the resin can be attributed to colloids formed owing to the high concentrations of Al and S in Acc. Sorption studies with the same radionuclides on hardened cement paste (HCP) in the presence of concrete admixture solutions and pore fluids squeezed from cement pastes further revealed no significant effect on sorption by either the concrete admixtures or their degradation products that were potentially present in the pore fluids. This finding suggests that the investigated concrete admixtures (PNS, PCE, Acc) and their degradation products have no significant impact on radionuclide mobilisation.