No abstract

The aggregation process, particularly the type and extent of pyronin Y (PY) laser dye intercalated into supported thin films of two different trioctahedral clay minerals, LAPONITE® (Lap) and saponite (Sap), at different dye loadings is studied: (i) experimentally by means of electronic absorption and fluorescence spectroscopy and (ii) theoretically by modeling the distribution of the dye into the interlayer space of these layered silicates. According to the results, H-type aggregates of the PY dye are favoured in Lap even at very low dye loading while a much lower molecular aggregation tendency in J-type geometry is found in Sap films. The aggregation state of PY in each clay mineral is likely attributed to different strengths of the electrostatic interactions between the dye and the layered silicate in the interlayer space due to their distinctive charge localization on the TOT clay layer (i.e. net negative charge in octahedral layers for Lap vs. in tetrahedral layers for Sap), as well as the interlaminar water distribution in each clay mineral, although other factors such as their CEC and particle size cannot be discarded. To reduce the huge aggregation processes of PY dye into Lap films, surfactant molecules (DDTAB) are co-adsorbed in the interlayer space of the clay. At an optimized surfactant concentration, the aggregation tendency of PY dye in Lap is considerably reduced enormously improving the fluorescence efficiency of the PY/Lap films. Finally, by means of anisotropic response from the hybrid films to the plane of the polarized light, the orientation of the PY molecules with respect to the normal axis of the clay layer is determined for all films (with and without surfactant) at different dye loadings.

Hybrid materials based on photoactive molecules confined into nanostructured substrates are very promising for technological applications. However, little is known about the impact of organic dyes on the mechanical properties of the substrate, a key aspect for their practical implementation. In this work, we use atomistic simulation methods to investigate the mechanical properties of two hybrid systems consisting on a clay matrix (laponite) loaded with two different cationic dyes (LDS-722 and pyronin Y). We applied tensile and shear deformations to the layered hybrid materials and characterize the key mechanism triggering their failure. It has been observed that the water and dye molecules located in the interlaminar spaces are those involved in the deformation processes, while the structure of the laponite layers does not change. Furthermore, it has been also found that the incorporation of dye molecules modifies the hydrogenbonding network of water in the interlaminar space, worsening the mechanical properties of the hybrids with respect to the clay. The information obtained by molecular simulation help us to assess the mechanical behavior of these materials, and to design materials with tailored strength.

Cementation is a widespread technique to immobilize nuclear waste due to the low leachability of cementitious materials. The capacity of calcium silicate hydrate (C-S-H), the main component of cement, to retain radionuclide Cs has been empirically studied at the macroscale, yet the specific molecular scale mechanisms that govern the retention have not been determined. In this work, we employed molecular dynamics simulations to investigate the adsorption and diffusivity of Cs into a C-S-H gel nanopore. From the simulations, it was possible to distinguish three types of Cs adsorption configurations on the C-S-H: an inner-sphere surface site where Cs is strongly bound, an outer-sphere surface site where Cs is loosely bound, and Cs free in the nanopore. For each configuration, we determined the sorption energy, and the diffusion coefficients, up to two orders of magnitude lower than in bulk water due to the effect of nanoconfinement in the worst case scenario. It has also proved that Cs cannot displace the intrinsic Ca from the C-S-H surface, and we calculated the binding strength and the residence time of the cations in the surface adsorption sites. Finally, we quantified the average number of adsorption sites per nm2 of the C-S-H surface. All these results are the first insights into Cs retention in cement at the molecular scale and will be useful to build macroscopic diffusion models and devise cement formulations to improve radionuclide Cs retention from spent nuclear fuel.