Conformation and association of confined anionic and cationic lithium mineral collectors in saltwater: Insights from, molecular dynamics simulations Q. Gonzalo, R.E. Roberto, and T.G. Pedro

Anionic surfactants, such as oleic acid and sodium oleate (OLE), and cationic surfactants, such as dodecyl amine-hydrochloride (DDA), are used as flotation collectors of spodumene. However, recovery is poor even if activating ions are used because gangue minerals are also activated. Some reports demonstrate that OLE/DDA mixtures act as a selective collector to enhance spodumene recovery. From mostly macroscopic tests, it has been argued that anionic OLE and cationic DDA form electroneutral complexes, which are adsorbed on the mineral surface through chemisorption; however, no molecular evidence has been presented. Therefore, the adsorption mechanisms of the collector mixtures remain mostly unknown. It seems necessary to first study the behaviour of these surfactants confined in salt solutions, to determine auto-associations when they are pure and cross-associations when mixed, the transition from monomers to micelles, and the structure of the micelles and the effects of pH, temperature and concentration. In this paper, ab initio calculations are first used to determine the surface charge distribution of OLE and DDA separately. Then molecular dynamics simulations are used to determine the conformation, aggregation, and diffusion of these pure and mixed surfactants in freshwater and saltwater with the ionic strength of seawater in a pH range. In particular, it is interesting to determine the various associations that result in mixtures of both surfactants and the impact of alkali and alkaline earth metal cations on the structures formedp. Cations influence the order of the structure and orientation of water dipoles, reducing the mobility of water, ions, and surfactant molecules. This knowledge is critical to improve the molecular understanding of the adsorption mechanisms on minerals. Keywords: Computer simulation, molecular dynamics, flotation, collectors, saltwater