With the aim of developing Pb-free Bi
2O
3-based new solder glasses; glass forming region, glass transition temperature, crystallization temperature, thermal expansion, and water resistance of Bi
2O
3-BaO-B
2O
3 ternary glass system were investigated. The roles of Bi
2O
3 in this ternary glass were also discussed. The results showed that glass transition temperature and thermal expansion coefficients of the ternary glasses were in similar range as compared to those solder glass consisting PbO. The water resistance of ternary glass was almost the same as compared to window glass, but it is higher than solder glass containing PbO. The glass transition temperature of ternary glass was dependent on average bond strength. Our results also showed that as the amount of Bi
2O
3 increased, the average bond strength was decreased which lead to decrement of glass transition temperature. These results suggested that Bi
2O
3 plays an important role as glass network former in the glass system.
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