Effects of <i>Re</i> ³⁺ radius on phase composition and thermal sensitivity of Ba _4.5 Re ₉ Ti ₁₈ O ₅₄ ceramics

Abstract Tungsten‐bronze materials are widely used in the fields of electro‐optic, photorefractive, pyroelectric, millimeter‐wave, and piezoelectric devices. In particular, tungsten‐bronze Ba 4.5 Sm 9 Ti 18 O 54 is believed to be useful for fabricating high‐temperature thermistors owing to its semiconductor properties. However, inherent shortcomings such as poor linearity (electrical properties deviate from the Arrhenius equation) and high aging coefficients limit the practical applications of these materials. Incorporating rare‐earth ( Re ) ions is an effective means of improving the electrical properties of thermistor materials. In this study, we explore the phase composition and thermosensitive properties of Ba 4.5 Re 9 Ti 18 O 54 (Re = Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu) ceramics with tungsten–bronze structures. The results indicate that the tungsten–bronze phase (Ba 4.5 Re 9 Ti 18 O 54 ) is generated when the radius of the Re 3+ ion exceeds 1.04 Å and the tolerance factor surpasses 0.82. Conversely, a pyrochlore phase (Re 2 Ti 2 O 7 ) accompanied by a monoclinic impurity phase (BaTi 2 O 5 ), is formed. Moreover, all Ba 4.5 Re 9 Ti 18 O 54 ceramics with a tungsten‐bronze structure exhibit exceptional linear electrical properties ( R 2 ≥ 999.09‰) and high sensitivity coefficients ( α 1000°C ≥ −0.79%/K). In particular, after aging at 1100°C for 600 h, both the aging coefficient and drift rate of material constant are as low as 5.76% and 1.79%, respectively. These results indicate that Ba 4.5 Re 9 Ti 18 O 54 ceramics are promising for high‐temperature and high‐accuracy temperature measurements.