We reveal the microscopic vacancy trapping mechanism for H bubble formation in W based on first-principles calculations of the energetics of H-vacancy interaction and the kinetics of H segregation. Vacancy provides an isosurface of optimal charge density that induces collective H binding on its internal surface, a prerequisite for the formation of ${\text{H}}_2$ molecule and nucleation of H bubble inside the vacancy. The critical H density on the vacancy surface before the ${\text{H}}_2$ formation is found to be ${10}^{19}–{10}^{20}\text{H}$ atoms per ${\text{m}}^2$. We believe that such mechanism is generally applicable for H bubble formation in metals and metal alloys.

Using a first-principles computational tensile test, we show that the ideal tensile strength of an Al grain boundary (GB) is reduced with both Na and Ca GB segregation. We demonstrate that the fracture occurs in the GB interface, dominated by the break of the interfacial bonds. Experimentally, we further show that the presence of Na or Ca impurity, which causes intergranular fracture, reduces the ultimate tensile strength when embrittlement occurs. These results suggest that the $\mathrm{Na}∕\mathrm{Ca}$-induced intergranular embrittlement of an Al alloy originates mainly from the GB weakening due to the $\mathrm{Na}∕\mathrm{Ca}$ segregation.

When an impurity is doped in a solid, it inevitably induces a local stress, tending to expand or contract the lattice. Consequently, strain can be applied to change the solubility of impurity in a solid. Generally, the solubility responds to strain “monotonically,” increasing (decreasing) with the tensile (compressive) strain if the impurity induces a compressive stress or vice versa. Using first-principles calculations, however, we discovered that the H solubility can be enhanced by anisotropic strain in some bcc metals, almost independent of the sign of strain. This anomalous behavior is found to be caused by a continuous change of H location induced by anisotropic strain. Our finding suggests a cascading effect of H bubble formation in bcc metals: the H solution leads to H bubble formation that induces anisotropic strain that in turn enhances H solubility to further facilitate bubble growth.

We have performed a first-principles computational tensile test on an aluminum grain boundary (GB) with sulfur segregation. We show that the tensile strength is reduced by 18% (to $7.80\mathrm{GPa}$) due to sulfur segregation in comparison with $9.50\mathrm{GPa}$ of the clean GB, and the GB fracture is caused by the interfacial bond breaking. We demonstrate the peculiar behavior of a sulfur-aluminum atom cluster at the interface during the tensile test, which originates from the intrinsic bonding characteristic of sulfur. Such cluster forms a one-dimensional chain structure that is similar to that in the bulk S, and remains unchanged in the tensile process until the fracture occurs but significantly changes the GB structure. This is responsible for the observed fact that the segregated sulfur atom bonds strongly with only a few of its neighboring aluminum atoms, leading to weaker interfacial aluminum-sulfur bonds. We suggest that the experimentally observed aluminum intergranular embrittlement is induced by the GB weakening due to sulfur segregation.

Combined density functional theory and empirical-potential calculations are performed to investigate the lowest-energy sites and migration mechanisms of He in various $$\alpha${}$-Fe grain boundaries (GBs). Before the defect calculations, we show that structural optimizations, including simulated annealing and atom removal, are crucial for locating the stable GB structure in a given temperature regime. Then, the He formation energies for all the substitutional and interstitial sites in two different GBs are evaluated, showing a strong He segregation tendency. At variance with the bulk Fe case, the formation energy of an interstitial He is either lower than or similar to that of a substitutional He in the GBs. Finally, both static and dynamic barriers for interstitial He diffusion in the GBs are determined. Although the diffusion details and precise paths are GB dependent, some common features are identified: (1) The He atom always remains confined to the GB region while diffusing; (2) the He diffusion is highly anisotropic along the GBs; (3) the GB diffusion of an interstitial He atom is found to be always slower than its bulk diffusion, but it can still be faster than the bulk diffusion of a substitutional He.

Doppler broadening spectroscopy in the positron annihilation technique (DBS-PA) has been employed to investigate the defect properties in argon-damaged tungsten exposed to low-energy and high flux deuterium plasma. Argon ion irradiations with energy 500 keV are performed for tungsten samples with various levels of damage. The remarkable increment of the S parameter in DBS-PA indicates the introduction of vacancy-type defects in argon irradiated tungsten. An increase of ion fluence results in a continuous increase of the S parameter until saturation. Unexpectedly, a much higher fluence leads to a decrease of the S parameter in the near surface, and the (S,W) slope changes greatly. This should be associated with the formation of argon-vacancy complexes in the near surface produced by the excessive implanted argon ions. With deuterium plasma exposure, a significant decrease of the S parameter occurs in the pre-irradiated tungsten, suggesting the sharp reduction of the number and density of the vacancy-type defects. The thermal desorption spectroscopy results demonstrate that the argon-damaged tungsten, compared to the pristine one, exhibits an enhanced low-temperature desorption peak and an additional and broad high-temperature desorption peak, which indicates that deuterium atoms are trapped in both low-energy and high-energy sites. All these observations directly indicate the deuterium occupation of irradiation-induced vacancy defects in damaged tungsten, which is responsible for the remarkable increase of the deuterium retention in comparison with the pristine one.