Structures of fluoride containing aluminosilicate low activity nuclear waste glasses: A molecular dynamics simulations study

Abstract Fluorine and other halides commonly exist in nuclear waste forms, and due to their volatile nature, halide retention poses an issue affecting waste loading during vitrification. The compositional effect on fluorine incorporation in aluminosilicate glasses is investigated through molecular dynamics simulations. Oxygen and fluorine coordination numbers around glass former and modifier cations, bond angle distributions, and medium range structure features such as Qn distributions, ring size distributions and neutron diffraction structure factors were calculated. It was found that fluorine has higher preference to bond to Ca2+ than to Na+, both in the melt and the glass, and there is no Si-F bond formation in the glass but they do exist in the melt. Consequently, CaO for Na2O substitution can be an effective way to help fluorine retention without significantly changing the glass chemistry. These results thus provide insights on fluorine incorporation in the aluminosilicate nuclear waste glasses and the strategy on how to improve fluorine retention both in the glass and the melt.