Pretransitional multiscale structure preceding third-phase formation in solvent extraction systems

Guerinoni, E.*; 上田 祐生   ; 元川 竜平   ; Zemb, T.*; Pellet-Rostaing, S.*; Dourdain, S.*

Guerinoni, E.*; Ueda, Yuki; Motokawa, Ryuhei; Zemb, T.*; Pellet-Rostaing, S.*; Dourdain, S.*

Third phase formation in liquid-liquid extraction poses operational challenges by inducing organic phase separation, limiting extraction efficiency and process safety. Here, we employ combined ultra-small-angle X-ray (USAXS) and neutron scattering (USANS) to elucidate pre-transitional structures occurring during uranium extraction by tri-octylamine (TOA) in octane as diluent. SAXS highlights uranium-filled aggregates, while SANS captures all aggregates, regardless of uranium content. Extending the q-range from 0.004 to 3 reveals two distinct populations: small spherical reverse micelle-like aggregates (radius 11 AA) and larger fluctuating domains exceeding 150 nm, consistent with Ornstein-Zernike critical fluctuations. Increasing TOA concentration amplifies these superstructures until divergence, the formation of a third phase. This study demonstrates that phase instability originates from the hierarchical condensation of water-filled aggregates around uranium-filled aggregates, rather than from simple micelle growth. Predicting such instability therefore requires accounting for the complete distribution of species, including water. The U-U distance in neighboring aggregate forming a supercluster is evidenced without ambiguity. Understanding such multiscale pre-transitional phenomena offers new routes to predict and mitigate phase separation in solvent extraction processes critical for nuclear fuel recycling.