Mechanics of colloidal supraparticles under compression.

Colloidal supraparticles are finite, spherical assemblies of many primary particles. To take advantage of their emergent functionalities, such supraparticles must retain their structural integrity. Here, we investigate their size-dependent mechanical properties via nanoindentation. We find that the deformation resistance inversely scales with the primary particle diameter, while the work of deformation is dependent on the supraparticle diameter. We adopt the Griffith theory to such particulate systems to provide a predictive scaling to relate the fracture stress to the geometry of supraparticles. The interplay between primary particle material and cohesive interparticle forces dictates the mechanical properties of supraparticles. We find that enhanced stability, associated with ductile fracture, can be achieved if supraparticles are engineered to dissipate more energy via deformation of primary particles than breaking of interparticle bonds. Our work provides a coherent framework to analyze, predict, and design the mechanical properties of colloidal supraparticles.

High-pressure synthesis of ultraincompressible hard rhenium nitride pernitride Re2(N2)(N)2 stable at ambient conditions.

High-pressure synthesis in diamond anvil cells can yield unique compounds with advanced properties, but often they are either unrecoverable at ambient conditions or produced in quantity insufficient for properties characterization. Here we report the synthesis of metallic, ultraincompressible (K0 = 428(10) GPa), and very hard (nanoindentation hardness 36.7(8) GPa) rhenium nitride pernitride Re2(N2)(N)2. Unlike known transition metals pernitrides Re2(N2)(N)2 contains both pernitride N24- and discrete N3- anions, which explains its exceptional properties. Re2(N2)(N)2 can be obtained via a reaction between rhenium and nitrogen in a diamond anvil cell at pressures from 40 to 90 GPa and is recoverable at ambient conditions. We develop a route to scale up its synthesis through a reaction between rhenium and ammonium azide, NH4N3, in a large-volume press at 33 GPa. Although metallic bonding is typically seen incompatible with intrinsic hardness, Re2(N2)(N)2 turned to be at a threshold for superhard materials.

Conical Nanoindentation Allows Azimuthally Independent Hardness Determination in Geological and Biogenic Minerals.

The remarkable mechanical performance of biominerals often relies on distinct crystallographic textures, which complicate the determination of the nanohardness from indentations with the standard non-rotational-symmetrical Berkovich punch. Due to the anisotropy of the biomineral to be probed, an azimuthal dependence of the hardness arises. This typically increases the standard deviation of the reported hardness values of biominerals and impedes comparison of hardness values across the literature and, as a result, across species. In this paper, we demonstrate that an azimuthally independent nanohardness determination can be achieved by using a conical indenter. It is also found that conical and Berkovich indentations yield slightly different hardness values because they result in different pile-up behaviors and because of technical limitations on the fabrication of perfectly equivalent geometries. For biogenic crystals, this deviation of hardness values between indenters is much lower than the azimuthal variation in non-rotational-symmetrical Berkovich indentations.