Substantially enhanced plasticity of bulk metallic glasses by densifying local atomic packing

Introducing regions of looser atomic packing in bulk metallic glasses (BMGs) was reported to facilitate plastic deformation, rendering BMGs more ductile at room temperature. Here, we present a different alloy design approach, namely, doping the nonmetallic elements to form densely packed motifs. The enhanced structural fluctuations in Ti-, Zr- and Cu-based BMG systems leads to improved strength and renders these solutes’ atomic neighborhoods more prone to plastic deformation at an increased critical stress. As a result, we simultaneously increased the compressive plasticity (from ∼8% to unfractured), strength (from ∼1725 to 1925 MPa) and toughness (from 87 ± 10 to 165 ± 15 MPa√m), as exemplarily demonstrated for the Zr20Cu20Hf20Ti20Ni20 BMG. Our study advances the understanding of the atomic-scale origin of structure-property relationships in amorphous solids and provides a new strategy for ductilizing BMG without sacrificing strength.

Tutorial on Chemical Pressure Analysis: How Atomic Packing Drives Laves/Zintl Intergrowth in K3Au5Tl

The tight atomic packing generally exhibited by alloys and intermetallics can create the impression of their being composed of hard spheres arranged to maximize their density. As such, the atomic size factor has historically been central to explanations of the structural chemistry of these systems. However, the role atomic size plays structurally has traditionally been inferred from empirical considerations. The recently developed DFT-Chemical Pressure (CP) analysis has opened a path to investigating these effects with theory. In this article, we provide a step-by-step tutorial on the DFT-CP method for non-specialists, along with advances in the approach that broaden its applicability. A new version of the CP software package is introduced, which features an interactive system that guides the user in preparing the necessary electronic structure data and generating the CP scheme, with the results being readily visualized with a web browser (and easily incorporated into websites). For demonstration purposes, we investigate the origins of the crystal structure of K3Au5Tl, which represents an intergrowth of Laves and Zintl phase domains. Here, CP analysis reveals that the intergrowth is supported by complementary CP features of NaTl-type KTl and MgCu2-type KAu2 phases. In this way, K3Au5Tl exemplifies how CP effects can drive the merging for geometrical motifs derived from different families of intermetallics through a mechanism referred to as epitaxial stabilization.

Expanding Monomers as Anti-Shrinkage Additives

Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a (significantly shorter) covalent bond. This volumetric shrinkage can have severe influence on the materials’ properties. One strategy to overcome this volumetric shrinkage is the use of expanding monomers that show volumetric expansion during polymerization reactions. Such monomers exhibit cyclic or even oligocyclic structural motifs with a correspondingly dense atomic packing. During the ring-opening reaction of such monomers, linear structures with atomic packing of lower density are formed, which results in volumetric expansion or at least reduced volumetric shrinkage. This review provides a concise overview of expanding monomers with a focus on the elucidation of structure-property relationships. Preceded by a brief introduction of measuring techniques for the quantification of volumetric changes, the most prominent classes of expanding monomers will be presented and discussed, namely cycloalkanes and cycloalkenes, oxacycles, benzoxazines, as well as thiocyclic compounds. Spiroorthoesters, spiroorthocarbonates, cyclic carbonates, and benzoxazines are particularly highlighted.

Protein Structure Refinement Guided by Atomic Packing Frustration Analysis

1AbstractRecent advances in machine learning, bioinformatics and the understanding of the folding problem have enabled efficient predictions of protein structures with moderate accuracy, even for targets when there is little information from templates. All-atom molecular dynamics simulations provide a route to refine such predicted structures, but unguided atomistic simulations, even when lengthy in time, often fail to eliminate incorrect structural features that would allow the structure to become more energetically favorable owing to the necessity of making large scale motions and overcoming energy barriers for side chain repacking. In this study, we show that localizing packing frustration at atomic resolution by examining the statistics of the energetic changes that occur when the local environment of a site is changed allows one to identify the most likely locations of incorrect contacts. The global statistics of atomic resolution frustration in structures that have been predicted using various algorithms provide strong indicators of structural quality when tested over a database of 20 targets from previous CASP experiments. Residues that are more correctly located turn out to be more minimally frustrated than more poorly positioned sites. These observations provide a diagnosis of both global and local quality of predicted structures, and thus can be used as guidance in all-atom refinement simulations of the 20 targets. Refinement simulations guided by atomic packing frustration turn out to be quite efficient and significantly improve the quality of the structures.