Despite their transformative role in our society, oxide glasses remain brittle. Although extrinsic postprocessing techniques can partially mitigate this drawback, they come with undesirable side effects. Alternatively, topological engineering offers an attractive option to enhance the intrinsic strength and damage resistance of glass. On the basis of this approach, we report here the discovery of a novel melt-quenched lithium aluminoborate glass featuring the highest crack resistance ever reported for a bulk oxide glass. Relying on combined mechanical and structural characterizations, we demonstrate that this unusual damage resistance originates from a significant self-adaptivity of the local atomic topology under stress, which, based on a selection of various oxide glasses, is shown to control crack resistance. This renders the lithium aluminoborate glass a promising candidate for engineering applications, such as ultrathin, yet ultrastrong, protective screens.

Sodium aluminoborate glasses are found to exhibit favorable mechanical properties, especially high crack resistance, due to their relatively low resistance to network compaction during sharp-contact loading. We here reveal the origin of the high crack resistance by investigating changes in structure and mechanical properties in compositions ranging from peralkaline to peraluminous and by varying the pressure history through an isostatic N 2-mediated pressure treatment at elevated temperature. This approach allows us to study the composition dependence of the ease of the glassy network compaction and the accompanying changes in structure and properties, which shed light on the processes occurring during indentation. Through solid state NMR measurements, we show that the network densification involves an increase in the average coordination number of both boron and aluminum and a shortening of the sodium-oxygen bond length. These changes in the short-range order of the glassy networks manifest themselves as an increase in, e.g., density and indentation hardness. We also demonstrate that the glasses most prone to network compaction exhibit the highest damage resistance, but surprisingly the crack resistance scales better with the relative density increase achieved by the hot compression treatment rather than with the extent of densification induced by indentation. This suggests that tuning the network structure may lead to the development of more damage resistant glasses, thus addressing the main drawback of this class of materials.

No abstract

No abstract

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.

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.

No abstract

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.