Competitive effects of modifier charge and size on mechanical and chemical resistance of aluminoborate glasses

Lithium aluminoborate glasses exhibit high resistance to cracking under contact loading, but low hardness and poor chemical durability in aqueous media. On the other hand, alkaline earth aluminoborate glasses feature improved chemical resistance and hardness, but lower resistance to cracking. In this work, we investigate the possibility to simultaneously improve the mechanical and chemical resistance of aluminoborate glasses by mixing alkali and alkaline earth modifiers. We study the mixed Li/Ba and Li/Mg aluminoborate glasses, since Li ⁺ and Ba ²⁺ have different charge and size but similar modifier field strength (charge to size ratio), while Mg ²⁺ has the highest field strength among these modifiers due to its small size. The two glass series will thus give insights into the competitive effects of modifier charge and size on glass structure, mechanical properties, and dissolution rates in acidic, neutral, and basic solutions. The substitution of barium for lithium at fixed [Al ₂O ₃]/[B ₂O ₃] ratio does not affect the network structure and properties, such as hardness and dissolution rate. However, the substitution of magnesium for lithium leads to an increase in hardness and chemical durability for all pH solutions (2, 7, and 14), likely as a result of the increase in the fractions of five- and six-fold coordinated aluminum species and atomic packing density. The glass with 5 mol% Li ₂O and 20 mol% MgO exhibits the best combination of high hardness and low dissolution rate, while maintaining a good crack-resistance comparable to that of the Li-aluminoborate glass. In both mixed glass series, the lowest dissolution rates are measured in neutral solutions, while those in acidic and especially basic media are higher. The structural origins of the trends in chemical and mechanical properties are discussed based on ¹¹B and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy measurements.