| Summary: | The effect of partial SiO<sub>2</sub> substitution with Al<sub>2</sub>O<sub>3</sub> and B<sub>2</sub>O<sub>3</sub> on the thermal properties and crystallization of glass sealants in the (50 − <i>x</i>)SiO<sub>2</sub>–30BaO–20MgO–<i>x</i>Al<sub>2</sub>O<sub>3</sub>(B<sub>2</sub>O<sub>3</sub>) (wt %) system is studied. It is established that the coefficient of thermal expansion of all obtained glasses lies within a range of 8.2–9.9 × 10<sup>−6</sup> K<sup>−1</sup>. Alumina-doped glasses crystallize after quenching, while samples containing boron oxide are completely amorphous. Magnesium silicates are formed in all glasses after exposure at 1000 °C for 125 h. After 500 h of exposure, a noticeable diffusion of zirconium ions is observed from the YSZ electrolyte to the glass sealant volume, resulting in the formation of the BaZrSi<sub>3</sub>O<sub>9</sub> compound. The crystallization and products of interaction between YSZ ceramics and boron-containing sealants have no significant effects on the adhesion and properties of glass sealants, which makes them promising for applications in electrochemical devices.
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