Direct imaging of short-range order and its impact on deformation in Ti-6Al.

Chemical short-range order (SRO) within a nominally single-phase solid solution is known to affect the mechanical properties of alloys. While SRO has been indirectly related to deformation, direct observation of the SRO domain structure, and its effects on deformation mechanisms at the nanoscale, has remained elusive. Here, we report the direct observation of SRO in relation to deformation using energy-filtered imaging in a transmission electron microscope (TEM). The diffraction contrast is enhanced by reducing the inelastically scattered electrons, revealing subnanometer SRO-enhanced domains. The destruction of these domains by dislocation planar slip is observed after ex situ and in situ TEM mechanical testing. These results confirm the impact of SRO in Ti-Al alloys on the scale of angstroms. The direct confirmation of SRO in relationship to dislocation plasticity in metals can provide insight into how the mechanical behavior of concentrated solid solutions by the material's thermal history.

Mechanical Enhancement of Bioinspired Polydopamine Nanocoatings.

Inspired by the catechol and amine-rich adhesive proteins of mussels, polydopamine (pDA) has become one of the most widely employed methods for functionalizing material surfaces, powered in part by the versatility and simplicity of pDA film deposition that takes place spontaneously on objects immersed in an alkaline aqueous solution of dopamine monomer. Despite the widespread adoption of pDA as a multifunctional coating for surface modification, it exhibits poor mechanical performance. Attempts to modify the physical properties of pDA by incorporation of oxidizing agents, cross-linkers, or carbonization of the films at ultrahigh temperatures have been reported; however, improving mechanical properties with mild post-treatments without sacrificing the functionality and versatility of pDA remains a challenge. Here, we demonstrate thermal annealing at a moderate temperature (130 °C) as a facile route to enhance mechanical robustness of pDA coatings. Chemical spectroscopy, X-ray scattering, molecular force spectroscopy, and bulk mechanical analyses indicate that monomeric and oligomeric species undergo further polymerization during thermal annealing, leading to fundamental changes in molecular and bulk mechanical behavior of pDA. Considerable improvements in scratch resistance were noted in terms of both penetration depth (32% decrease) and residual depth (74% decrease) for the annealed pDA coating, indicating the enhanced ability of the annealed coating to resist mechanical deformations. Thermal annealing resulted in significant enhancement in the intermolecular and cohesive interactions between the chains in the pDA structure, attributed to cross-linking and increased entanglements, preventing desorption and detachment of the chains from the coating. Importantly, improvements in pDA mechanical performance through thermal annealing did not compromise the ability of pDA to support secondary coating reactions as evidenced by electroless deposition of a metal film adlayer on annealed pDA.

Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals.

Large, freestanding membranes with remarkably high elastic modulus (>10 GPa) have been fabricated through the self-assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures, which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. Thin-film buckling and nanoindentation are used to evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ∼6-19 GPa, and hardness of ∼120-170 MPa. We find that rapidly self-assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.

Assessment of lamellar level properties in mouse bone utilizing a novel spherical nanoindentation data analysis method.

In this work, we demonstrate the viability of using our recently developed data analysis procedures for spherical nanoindentation in conjunction with Raman spectroscopy for studying lamellar-level correlations between the local composition and local mechanical properties in mouse bone. Our methodologies allow us to convert the raw load-displacement datasets to much more meaningful indentation stress-strain curves that accurately capture the loading and unloading elastic moduli, the indentation yield points, as well as the post-yield characteristics in the tested samples. Using samples of two different inbred mouse strains, A/J and C57BL/6J (B6), we successfully demonstrate the correlations between the mechanical information obtained from spherical nanoindentation measurements to the local composition measured using Raman spectroscopy. In particular, we observe that a higher mineral-to-matrix ratio correlated well with a higher local modulus and yield strength in all samples. Thus, new bone regions exhibited lower moduli and yield strengths compared to more mature bone. The B6 mice were also found to exhibit lower modulus and yield strength values compared to the more mineralized A/J strain.