Observation of indentation-induced shear bands in a metal-organic framework glass

Metal-organic framework (MOF) glasses are a newly emerged family of melt-quenched glasses. Recently, several intriguing features, such as ultrahigh glass-forming ability and low liquid fragility, have been discovered in a number of zeolitic imidazolate frameworks (ZIFs) that are a subset of MOFs. However, the fracture behavior of ZIF glasses has not been explored. Here we report an observation of both cracking pattern and shear bands induced by indentation in a representative melt-quenched ZIF glass, that is, ZIF-62 glass (ZnIm_1.68bIm_0.32). The shear banding in the ZIF glass is in strong contrast to the cracking behavior of other types of fully polymerized glasses, which do not exhibit any shear bands under indentation. We attribute this anomalous cracking behavior to the easy breakage of the coordinative bonds (Zn-N) in ZIF glasses, since these bonds are much weaker than the ionic and covalent bonds in network glasses.