Frustrated Coulombic and Cation Size Effects on Nanoscale Boehmite Aggregation: A Tumbler Small- and Ultra-Small-Angle Neutron Scattering Study

LM Anovitz and P Huestis and N Rampal and AG Stack and JA LaVerne and X Zhang and GK Schenter and J Chun and BA Legg and L Liu and M Bleuel and C Gagnon and DFR Mildner, JOURNAL OF PHYSICAL CHEMISTRY C, 126, 4391-4414 (2022).

DOI: 10.1021/acs.jpcc.1c10580

To better understand the effects of solution chemistry on particle aggregation in the complex legacy tank wastes at the Hanford (WA) and Savannah River (SC) sites, we have performed a series of tumbler small- and ultra-small-angle neutron scattering experiments on 20 wt % solid slurries of nanoparticulate aluminum oxyhydroxide (boehmite) with M1+ nitrates of various concentrations and radii. The solutes consisted of H, Li, Na, K, and Rb nitrates at 10(-5), 10(-3), 10(-1), 2, and 4 molal (m) concentrations, as well as in pure H2O. Synthetic boehmite nanoparticles were used with a size range from similar to 20 to 30 nm. Tumbler cells were used to keep the solids from settling. Although particles initially form individual rhombohedral platelets, once placed in solution, they quickly form well-bonded stacks, primary aggregates, up to similar to 1500 angstrom long, and a second level of aggregates whose concentration and structure vary as a function of cation type and concentration. Aggregation generally increases with increased solute concentration and with cation radius up to a concentration somewhat above 10(-1) m, at which point the trend reverses. Primary aggregates become more rodlike and larger. The Kirkwood-like reversal probably reflects a change from Derjaguin-Landau-Verwey-Overbeek (DLVO)/Debye behavior controlled by surface chemistry to a frustrated Coulombic system controlled by the solution structure. These data suggest that an understanding of the effects of salt concentration and chemistry on nanoparticle aggregate structures provides useful physical insights into the microscopic origin of slurry rheology in the Hanford and Savannah River legacy wastes.

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