Structural phase transition and giant negative thermal expansion in pyrophosphate Zn2–xMgxP2O7

By tuning the structural phase transition in Zn2–xMgxP2O7, large negative thermal expansion (NTE) was achieved at room temperature. An earlier report described that Zn2P2O7 undergoes a structural phase transition at 405 K, accompanied by volume contraction of 1.8% on heating. Results showed that as Mg doping proceeds, the transition temperature decreases. Also, the volume change becomes gradual with respect to temperature. Particularly, Zn1.6Mg0.4P2O7 has a large negative coefficient of linear thermal expansion αL of −60 ppm/K at 280–350 K. Structural analysis using synchrotron radiation revealed that this dilatometric NTE is almost identical to that of crystallographic unit cells, indicating less dominant structural effects on NTE. We also verified thermal expansion compensation capabilities of powdered Zn1.6Mg0.4P2O7 by evaluating the thermal expansion of the epoxy resin matrix composites. The present phosphates are promising for use as practical thermal expansion compensators because they are free of toxic or expensive elements and can be fabricated in air using the simple solid-state reaction method.