The fracture toughness of glassy materials remains poorly understood. In large part, this is due to the disordered, intrinsically non-equilibrium nature of the glass structure, which challenges its theoretical description and experimental determination. We show that the notch fracture toughness of metallic glasses exhibits an abrupt toughening transition as a function of a well-controlled fictive temperature (Tf), which characterizes the average glass structure. The ordinary temperature, which has been previously associated with a ductile-to-brittle transition, is shown to play a secondary role. The observed transition is interpreted to result from a competition between the Tf-dependent plastic relaxation rate and an applied strain rate. Consequently, a similar toughening transition as a function of strain rate is predicted and demonstrated experimentally. The observed mechanical toughening transition bears strong similarities to the ordinary glass transition and explains the previously reported large scatter in fracture toughness data and ductile-to-brittle transitions.
Gene therapy promises to treat diseases that arise from genetic abnormalities by correcting the underlying cause of the disease rather than treating the associated symptoms. Successful transfer of nucleic acids into cells requires efficient delivery vehicles that protect the cargo and can penetrate the appropriate cellular barriers before releasing their contents. Many viral vectors and synthetic polycationic vectors for nucleic acid delivery do not translate well from in vitro to in vivo applications due to their instability and toxicity. We synthesized and characterized a library of biocompatible low charge density polymers from a family of poly(amine- co-ester) (PACE) terpolymers produced via enzyme catalyzed polymerization. PACE polymers are highly customizable; we found that the terpolymer composition can be optimized to produce efficient transfection of various nucleic acids-including DNA plasmids, mRNA, and siRNA-in specific cell types with low toxicity. Our findings suggest that the unique tunability of PACEs offers new tools for gene therapy and other biomedical applications.
Nanoimprinting by thermoplastic forming has attracted significant attention due to its promise of low-cost fabrication of functionalized surfaces and nanostructured devices, and metallic glasses have been identified as a material class ideally suited for nanoimprinting. In particular, their featureless atomic structure suggests that there may not be an intrinsic size limit to the material's ability to replicate a mould. Here we demonstrate atomic-scale imprinting into a platinum-based metallic glass alloy under ambient conditions using atomic step edges of a strontium titanate single crystal as a mould. The moulded metallic glass replicates the 'atomic smoothness' of the strontium titanate, with identical roughness to the one measured on the mould even after multiple usages and with replicas exhibiting an exceptional long-term stability of years. By providing a practical, reusable, and potentially high-throughput approach for atomic imprinting, our findings may open novel applications in surface functionalization through topographical structuring.
Because brittle solids fail catastrophically during normal tension and compression testing, nanoindentation is often a useful alternative technique for measuring their mechanical properties and assessing their deformation characteristics. One practical question to be addressed in such studies is the relationship between the anisotropy in the uniaxial mechanical behavior to that in the indentation response. To this end, a systematic study of the mechanical behavior the 6H polytype of a hexagonal silicon carbide single crystal (SiC-6H) was performed using standard nanoindentation methods. The indentation elastic modulus and hardness measured using a Berkovich indenter at a peak load of 500 mN varied over a wide range of crystal orientation by only a few percent. The variation in modulus is shown to be consistent with an anisotropic elastic contact analysis based on the known single crystal elastic constants of the material. The variation in hardness is examined using a single crystal plasticity model that considers the anisotropy of slip in hexagonal crystals. When compared to experimental measurements, the analysis confirms that plasticity in SiC-6H is dominated by basal slip. An anisotropic elastic contact analysis provides insights into the relationship between the pop-in load, which characterizes the transition from elasticity to plasticity during nanoindentation testing, and the theoretical strength of the material. The observations and analyses lay the foundations for further examination of the deformation and failure mechanisms in anisotropic materials by nanoindentation techniques.
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