Silver (Ag) is a precious metal with a low stacking fault energy that is known to form copious nanoscale coherent twin boundaries during magnetron sputtering synthesis. Nanotwinned Ag metals are potentially attractive for creating new interface-dominated nanomaterials with unprecedented mechanical and physical properties. Grain-boundary segregation of solute elements has been found to increase the stability of interfaces and hardness of nanocrystalline metals. However, heavily alloying inevitably complicates the underlying deformation mechanisms due to the hardening effects of solutes, or a change of stacking fault energies in Ag caused by alloying. For the above reasons, we developed a microalloying (or doping) strategy by carefully selecting Cu as the primary impurity – a solute that is predicted to have no solid-solution strengthening effect in Ag when its content is below 3.0 wt.%. Neither will Cu affect the stacking fault energy of Ag at a concentration <1.0 wt.%. Moreover, Cu atoms are ~12% smaller than Ag ones, and Ag-Cu is an immiscible system, which facilitates the segregation of Cu into high-energy interface sites such as grain-boundaries and twin-boundary defects. In this thesis, large-scale hybrid Monte-Carlo and molecular dynamics simulations are used to study the unexplored mechanical behavior of Cu-segregated nanocrystalline nanotwinned Ag. First, the small-scale mechanics of solute Cu segregation and its effects on incipient plasticity mechanisms in nanotwinned Ag were studied. It was found that solute Cu atoms are segregated concurrently to grain boundaries and intrinsic twin-boundary kink-step defects. Low segregated Cu contents (< 1 at.%) are found to substantially increase twin-defect stability, leading to a pronounced rise in yield strength at 300 K. Second, atomistic simulations with a constant grain size of 45 nm and a wide range of twin boundary spacings were performed to investigate the Hall-Petch strength limit in nanocrystalline nanotwinned Ag containing either perfect or kinked twin boundaries. Three distinct strength regions were discovered as twin boundary decreases, delineated by normal Hall-Petch strengthening with a positive slope, the grain-boundary-dictated mechanism with near-zero Hall-Petch slope, and twin-boundary defect induced softening mechanism with a negative Hall-Petch slope. Third, by systematically studying smaller grain sizes, we find that the “strongest” size for pure nanotwinned Ag is achieved for a grain size of ~16 nm, below which softening occurs. The controlling plastic deformation mechanism changes from dislocation nucleation to grain boundary motion. This transition decreases to smaller grain sizes when Cu contents are segregated to the interfaces. Our simulations show that continuous Hall-Petch strengthening without softening, down to grain sizes as small as 6 nm, is reached when adding Cu atoms up to 12 at. %. For Cu contents ≥ 15 at. %, however, the predominant plastic deformation mechanism changes to shear-band induced softening. The present thesis provides new fundamental insights into solute segregation, and strengthening mechanisms mediated by grain boundaries and twin boundaries in face-centered cubic Ag metals, which is expected to motivate experimental studies on new nanotwinned metals with superior mechanical properties controlled by microalloying.

<p>  </p> <p>Aluminum (Al) possesses a plenitude of remarkable properties, such as strong corrosion resistance, high thermal and electrical conductivity, and high specific strength. However, Al and its alloys are still remarkably weaker than most high strength steels and susceptible to drastic softening at high temperatures, preventing many applications where its low density would be beneficial. Severe plastic deformation can yield ultra-fine grained Al alloys with similar strengths as steels, although they are highly unstable even at room temperature. Nanotwinned (NT) metals have demonstrated concomitant strength and ductility, enabled by twin boundaries which simultaneously act to inhibit dislocation motion and generate partial dislocations that aid in plasticity. In spite of having a high stacking fault energy, nanotwins have been introduced into Al alloys using transition metal solutes during magnetron sputtering. This thesis aims to explore the impact Zr has on the microstructure, deformation, and thermal stability of nanotwins in NT Al.</p> <p>Our studies identify how Zirconium (Zr) aids in the formation of a significant volume fraction of 9R phase and an abundance of finely spaced incoherent twin boundaries, leading to a maximum hardness of 4.2GPa. They further uncover through <em>in-situ</em> micropillar compression that NT Al-Zr alloys are highly deformable and reach a flow stress of ~1.1GPa. Constant strain rate nanoindentation tests demonstrate the enhanced strain rate sensitivity in NT Al-Zr alloys. Zr is also identified to be a remarkable thermal stabilizer when incorporated into NT Al-Co alloys, with no apparent softening up to 450 °C (0.78 T­m). The influence of substrate texture on nanotwinned Al-Zr alloys microstructure was also thoroughly explored.</p>