Over the past several decades, research on anomalous thermal expansion materials has been rapidly growing, and increasing numbers of compounds exhibiting negative thermal expansion (NTE) have been reported. In particular, compounds with formula A₂M₃O₁₂ have attracted considerable attention. A₂M₃O₁₂ family materials offer a wide range of possible compositions due to the chemical flexibility of the A and M sites. According to published research, more than half of them possess NTE properties. This paper reviews the range of physical properties displayed by materials in the A₂M₃O₁₂ family. Research on improving material imperfections and controlling the coefficient of thermal expansion in the A₂M₃O₁₂ family are systematically summarized. Finally, challenges and questions about the developments of these A₂M₃O₁₂ NTE compounds in future studies are also discussed.

Zr₂WP₂O₁₂/ZrO₂ composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr₂WP₂O₁₂/ZrO₂ composites with different mass ratio. Relative densities of all the resulting Zr₂WP₂O₁₂/ZrO₂ samples were also tested by Archimedes' methods. The obtained Zr₂WP₂O₁₂/ZrO₂ composites were comprised of orthorhombic Zr₂WP₂O₁₂ and monoclinic ZrO₂. As the increase of the Zr₂WP₂O₁₂, the relative densities of Zr₂WP₂O₁₂/ZrO₂ ceramic composites increased gradually. The coefficient of thermal expansion of the Zr₂WP₂O₁₂/ZrO₂ composites can be tailored from 4.1 × 10⁻⁶ K⁻¹ to −3.3 × 10⁻⁶ K⁻¹ by changing the content of Zr₂WP₂O₁₂. The 2:1 Zr₂WP₂O₁₂/ZrO₂ specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of −0.09 × 10⁻⁶ K⁻¹. These adjustable and near zero expansion ceramic composites will have great potential application in many fields.