Giant negative thermal expansion covering room temperature in nanocrystalline GaNxMn3

TL;DR

This study demonstrates giant negative thermal expansion in nanocrystalline GaNxMn3 compounds near room temperature, with tunable properties achieved through grain size reduction, promising for advanced thermal management applications.

Contribution

It reports the first observation of giant NTE in mechanically milled GaNxMn3, with significantly enhanced effects due to nanostructuring and grain size control.

Findings

Large volume contraction at AFM-PM transition within a narrow temperature window.

Coefficient of linear thermal expansion reaches ~ -70 ppm/K, nearly twice previous materials.

Giant NTE persists and is tunable with grain size reduction to ~10 nm.

Abstract

Materials with negative thermal expansion (NTE), which contract upon heating, are of great interest both technically and fundamentally. Here, we report giant NTE covering room temperature in mechanically milled antiperovksite GaNxMn3 compounds. The micrograin GaNxMn3 exhibits a large volume contraction at the antiferromagnetic (AFM) to paramagnetic (PM) (AFM-PM) transition within a temperature window ({\Delta}T) of only a few kelvins. The grain size reduces to ~ 30 nm after slight milling, while {\Delta}T is broadened to 50K. The corresponding coefficient of linear thermal expansion ({\alpha}) reaches ~ -70 ppm/K, which is almost two times larger than those obtained in chemically doped antiperovskite compounds. Further reducing grain size to ~ 10 nm, {\Delta}T exceeds 100 K and {\alpha} remains as large as -30 ppm/K (-21 ppm/K) for x = 1.0 (x = 0.9). Excess atomic displacements together with the reduced structural coherence, revealed by high-energy X-ray pair distribution functions, are suggested to delay the AFM-PM transition. By controlling the grain size via mechanically alloying or grinding, giant NTE may also be achievable in other materials with large lattice contraction due to electronic or magnetic phase transitions.