Additive-free superhard B4C with ultrafine-grained dense microstructures

A unique combination of high-energy ball-milling, annealing, and spark-plasma sintering has been used to process superhard B4C ceramics with ultrafine-grained, dense microstructures from commercially available powders, without sintering additives. It was found that the ultrafine powder prepared by high-energy ball-milling is hardly at all sinterable, but that B2O3 removal by gentle annealing in Ar provides the desired sinterability. A parametric study was also conducted to elucidate the role of the temperature (1600–1800 °C), time (1–9 min), and heating ramp (100 or 200 °C/min) in the densification and grain growth, and thus to identify optimal spark-plasma sintering conditions (i.e., 1700 °C for 3 min with 100 °C/min) to densify completely (>98.5%) the B4C ceramics with retention of ultrafine grains (∼370 nm). Super-high hardness of ∼38 GPa without relevant loss of toughness (∼3 MPa m1/2) was thus achieved, attributable to the smaller grain size and to the transgranular fracture mode of the B4C ceramics.