# First-Principles Multiscale Investigation of Structural and Chemical Defects in Metals

 Title: First-Principles Multiscale Investigation of Structural and Chemical Defects in Metals Author: Schusteritsch, Georg Citation: Schusteritsch, Georg. 2012. First-Principles Multiscale Investigation of Structural and Chemical Defects in Metals. Doctoral dissertation, Harvard University. Access Status: Full text of the requested work is not available in DASH at this time (“dark deposit”). For more information on dark deposits, see our FAQ. Full Text & Related Files: Schusteritsch_gsas.harvard_0084L_10586.pdf (4.504Mb; PDF) Abstract: This thesis explores multiscale approaches to describe structural and chemical defects in metals. Particular emphasis is placed on investigating processes involving grain boundaries (GBs) in combination with impurity and vacancy defects. The defects and their interactions are calculated to very high accuracy using density functional theory (DFT) and connected to the macroscopic behavior within the two multiscale formalisms presented here. We begin with a sequential approach to address chemical embrittlement of nickel by sulfur impurities. Effects at both a $$\Sigma 5 (012)$$ symmetric tilt GB and in the bulk are studied by considering competing mechanisms for ductile and brittle behavior. For the bulk, this takes the form of Rice’s theory, where the ratio of the surface and unstable stacking energy is used as a measure of ductility. This is generalized to the GB by considering GB sliding (GBS) and intergranular decohesion. Clear evidence that chemical embrittlement of nickel by sulfur is a GB driven effect is found. Next, a concurrent multiscale approach is described. A small region, containing the defects, is treated with Kohn-Sham DFT and coupled to the bulk, described with the embedded atom method. We apply this novel method to elucidate the chemical embrittlement of a copper $$\Sigma 5 (012)$$ symmetric tilt GB. Intergranular decohesion for three substitutional impurities, bismuth, lead and silver, is investigated by considering the work of separation $$(W_s)$$ and the tensile strength $$(\sigma_t)$$. Bismuth and lead show a significant decrease in $$W_s$$ and $$\sigma_t$$, consistent with embrittlement, whilst silver has only a minor effect. Then, the concurrent multiscale method is applied to the process of GBS in copper. It is found that the resistance against sliding increases significantly for bismuth, lead and silver impurities. The underlying mechanisms for this increase are found to be dominated by size effects for bismuth and lead. For silver, chemical effects are of greater importance. Similar results are found for the underlying mechanisms of intergranular decohesion. The effect of a mono-vacancy on GBS is studied for copper. The multiscale approach enables improved decoupling of the mono-vacancy. It is found that the monovacancy enhances GBS by 22%. Citable link to this page: http://nrs.harvard.edu/urn-3:HUL.InstRepos:10381389 Downloads of this work: