The lubricity of hydrogenated diamond-like carbon (HDLC) films is highly sensitive to the hydrogen (H) content in the film and the oxidizing gas in the environment. The tribochemical knowledge of HDLC films with two different H-contents (mildly hydrogenated vs highly hydrogenated) was deduced from the analysis of the transfer layers formed on the counter-surface during friction tests in O2 and H2O using Raman spectroscopic imaging and X-ray photoelectron spectroscopy (XPS). The results showed that, regardless of H-content in the film, shear-induced graphitization and oxidation take place readily. By analyzing the O2 and H2O partial pressure dependence of friction of HDLC with a Langmuir-type reaction kinetics model, the oxidation probability of the HDLC surface exposed by friction as well as the removal probability of the oxidized species by friction were determined. The HDLC film with more H-content exhibited a lower oxidation probability than the film with less H-content. The atomistic origin of this H-content dependence was investigated using reactive molecular dynamics simulations, which showed that the fraction of undercoordinated carbon species decreased as the H-content in the film increased, corroborating the lower oxidation probability of the highly-hydrogenated film. The H-content in the HDLC film influenced the probabilities of oxidation and material removal, both of which vary with the environmental condition.
The stabilization of supported nanoclusters is critical for different applications, including catalysis and plasmonics. Herein we investigate the impact of MoS2 grain boundaries (GBs) on the nucleation and growth of Pt NCs. The optimum atomic structure of the metal clusters is obtained using an adaptive genetic algorithm that employs a hybrid approach based on atomistic force fields and density functional theory. Our findings show that GBs stabilize the NCs up to a cluster size of nearly ten atoms, and with larger clusters having a similar binding to the pristine system. Notably, Pt monomers are found to be attracted to GB cores achieving 60% more stabilization compared to the pristine surface. Furthermore, we show that the nucleation and growth of the metal seeds are facile with low kinetic barriers, which are of similar magnitude to the diffusion barriers of metals on the pristine surface. The findings highlight the need to engineer ultrasmall NCs to take advantage of enhanced stabilization imparted by the GB region, particularly to circumvent sintering behavior for high-temperature applications.
Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe0.28Co0.21Ni0.20Cu0.08Pt0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner's theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe2O3, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.
