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 (ZnIm1.68bIm0.32). 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.

Breaking the Limit of Micro-Ductility in Oxide Glasses.

Oxide glasses are one of the most important engineering and functional material families owing to their unique features, such as tailorable physical properties. However, at the same time intrinsic brittleness has been their main drawback, which severely restricts many applications. Despite much progress, a breakthrough in developing ultra-damage-resistant and ductile oxide glasses still needs to be made. Here, a critical advancement toward such oxide glasses is presented. In detail, a bulk oxide glass with a record-high crack resistance is obtained by subjecting a caesium aluminoborate glass to surface aging under humid conditions, enabling it to sustain sharp contact deformations under loads of ≈500 N without forming any strength-limiting cracks. This ultra-high crack resistance exceeds that of the annealed oxide glasses by more than one order of magnitude, making this glass micro-ductile. In addition, a remarkable indentation behavior, i.e., a time-dependent shrinkage of the indent cavity, is demonstrated. Based on structural analyses, a molecular-scale deformation model to account for both the ultra-high crack resistance and the time-dependent shrinkage in the studied glass is proposed.

Revisiting the Dependence of Poisson's Ratio on Liquid Fragility and Atomic Packing Density in Oxide Glasses.

Poisson's ratio (ν) defines a material's propensity to laterally expand upon compression, or laterally shrink upon tension for non-auxetic materials. This fundamental metric has traditionally, in some fields, been assumed to be a material-independent constant, but it is clear that it varies with composition across glasses, ceramics, metals, and polymers. The intrinsically elastic metric has also been suggested to control a range of properties, even beyond the linear-elastic regime. Notably, metallic glasses show a striking brittle-to-ductile (BTD) transition for ν-values above ~0.32. The BTD transition has also been suggested to be valid for oxide glasses, but, unfortunately, direct prediction of Poisson's ratio from chemical composition remains challenging. With the long-term goal to discover such high-ν oxide glasses, we here revisit whether previously proposed relationships between Poisson's ratio and liquid fragility (m) and atomic packing density (Cg) hold for oxide glasses, since this would enable m and Cg to be used as surrogates for ν. To do so, we have performed an extensive literature review and synthesized new oxide glasses within the zinc borate and aluminoborate families that are found to exhibit high Poisson's ratio values up to ~0.34. We are not able to unequivocally confirm the universality of the Novikov-Sokolov correlation between ν and m and that between ν and Cg for oxide glass-formers, nor for the organic, ionic, chalcogenide, halogenide, or metallic glasses. Despite significant scatter, we do, however, observe an overall increase in ν with increasing m and Cg, but it is clear that additional structural details besides m or Cg are needed to predict and understand the composition dependence of Poisson's ratio. Finally, we also infer from literature data that, in addition to high ν, high Young's modulus is also needed to obtain glasses with high fracture toughness.

Structural Compromise between High Hardness and Crack Resistance in Aluminoborate Glasses.

Alkali aluminoborate glasses have recently been shown to exhibit a high threshold for indentation cracking compared to other bulk oxide glasses. However, to enable the use of these materials in engineering applications, there is a need to improve their hardness by tuning the chemical composition. In this study, we substitute alkaline earth for alkali network-modifying species at fixed aluminoborate base glass composition and correlate it with changes in the structure, mechanical properties, and densification behavior. We find that the increase in field strength (i.e., the charge-to-size ratio) achieved by substituting alkaline earth oxide from BaO to MgO manifests itself in a monotonic increase in several properties, such as atomic packing density, glass-transition temperature, densification ability, indentation hardness, and crack resistance. Although the use of alkaline earth oxides as modifier enables higher hardness values (increasing from 2.0 GPa for Cs to 5.8 GPa for Mg), their crack resistance is generally lower than that of the corresponding alkali aluminoborate glasses. We discuss the origin of this compromise between hardness and crack resistance in terms of the ability of the glass networks to undergo structural transformations and self-adapt under stress. We show that the extent of volume densification scales linearly with the number of pressure-induced coordination number changes of B and Al.