Controllable Negative Thermal Expansion by Mechanical Pulverizing in Hexagonal Mn_0.965Co_1.035Ge Compounds

Negative thermal expansion (NTE) material as a compensator is very important for accurately controlling the thermal expansion of materials. Along with the magnitude of the coefficient of thermal expansion, the operating temperature window of the NTE materials is also a major concern. However, only a few of the NTE materials possess both a large operating temperature range and a large thermal expansion coefficient. To explore this type of new NTE material, the Mn_0.965Co_1.035Ge fine powders were prepared by mechanical ball milling (BM). These fine powders show a largely extended NTE operation temperature window simultaneously possessing a giant thermal expansion coefficient. For samples treated with different BM times, such as the BM-0.5h, BM-4h, and BM-12 h samples, the operating temperature window (Δ T) and linear thermal expansion coefficient (α_L) are 167 K (222-389 K) and ∼ -63 ppm/K, 221 K (140-360 K) and ∼ -41.3 ppm/K, and 208 K (234-442 K) and ∼ -40 ppm/K, respectively, which are larger than most well-known NTE materials. More strikingly, all BM samples have a large constant linear NTE coefficient with an ultrawide temperature window covering room temperature. For these three samples, these values are ∼ -52 ppm/K (140 K), ∼ -58.3 ppm/K (110 K), and ∼ -65 ppm/K (80 K), respectively. The origin of the excellent NTE properties is discussed based on the thermomagnetic measurements and X-ray absorption spectroscopic results.