Brittle-to-ductile transition and theoretical strength in a metal–organic framework glass

Abstract

Metal–organic framework (MOF) glasses, a new type of melt–quenched glass, show great promise to deal with the alleviation of greenhouse effects, energy storage and conversion. However, the mechanical behavior of MOF glasses, which is of critical importance given the need for long-term stability, is not well understood. Using both micro- and nanoscale loadings, we find that pillars of a zeolitic imidazolate framework (ZIF) glass have a compressive strength falling within the theoretical strength limit of ≥E/10, a value which is thought to be unreachable in amorphous materials. Pillars with a diameter larger than 500 nm exhibited brittle failure with deformation mechanisms including shear bands and nearly vertical cracks, while pillars with a diameter below 500 nm could carry large plastic strains of ≥20% in a ductile manner with enhanced strength. We report this room-temperature brittle-to-ductile transition in ZIF-62 glass for the first time and demonstrate that theoretical strength and large ductility can be simultaneously achieved in ZIF-62 glass at the nanoscale. Large-scale molecular dynamics simulations have identified that microstructural densification and atomistic rearrangement, i.e., breaking and reconnection of inter-atomistic bonds, were responsible for the exceptional ductility. The insights gained from this study provide a way to manufacture ultra-strong and ductile MOF glasses and may facilitate their processing toward real-world applications.