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Despite the ubiquitous presence of passivation on most metal surfaces, the microscopic‐level picture of how surface passivation occurs has been hitherto unclear. Using the canonical example of the surface passivation of aluminum, here in situ atomistic transmission electron microscopy observations and computational modeling are employed to disentangle entangled microscopic processes and identify the atomic processes leading to the surface passivation. Based on atomic‐scale observations of the layer‐by‐layer expansion of the metal lattice and its subsequent transformation into the amorphous oxide, it is shown that the surface passivation occurs via a two‐stage oxidation process, in which the first stage is dominated by intralayer atomic shuffling whereas the second stage is governed by interlayer atomic disordering upon the progressive oxygen uptake. The first stage can be bypassed by increasing surface defects to promote the interlayer atomic migration that results in direct amorphization of multiple atomic layers of the metal lattice. The identified two‐stage reaction mechanism and the effect of surface defects in promoting interlayer atomic shuffling can find broader applicability in utilizing surface defects to tune the mass transport and passivation kinetics, as well as the composition, structure, and transport properties of the passivation films.

 

This study demonstrates an atomic composition manipulation on Pt–Ni nano-octahedra to enhance their electrocatalytic performance. By selectively extracting Ni atoms from the {111} facets of the Pt–Ni nano-octahedra using gaseous carbon monoxide at an elevated temperature, a Pt-rich shell is formed, resulting in an ∼2 atomic layer Pt-skin. The surface-engineered octahedral nanocatalyst exhibits a significant enhancement in both mass activity (∼1.8-fold) and specific activity (∼2.2-fold) toward the oxygen reduction reaction compared with its unmodified counterpart. After 20,000 potential cycles of durability tests, the surface-etched Pt–Ni nano-octahedral sample shows a mass activity of 1.50 A/mgPt, exceeding the initial mass activity of the unetched counterpart (1.40 A/mgPt) and outperforming the benchmark Pt/C (0.18 A/mgPt) by a factor of 8. DFT calculations predict this improvement with the Pt surface layers and support these experimental observations. This surface-engineering protocol provides a promising strategy for developing novel electrocatalysts with improved catalytic features. 

Purpose AlSi10Mg alloy is commonly used in laser powder bed fusion due to its printability, relatively high thermal conductivity, low density and good mechanical properties. However, the thermal conductivity of as-built materials as a function of processing (energy density, laser power, laser scanning speed, support structure) and build orientation, are not well explored in the literature. This study aims to elucidate the relationship between processing, microstructure, and thermal conductivity. Design/methodology/approach The thermal conductivity of laser powder bed fusion (L-PBF) AlSi10Mg samples are investigated by the flash diffusivity and frequency domain thermoreflectance (FDTR) techniques. Thermal conductivities are linked to the microstructure of L-PBF AlSi10Mg, which changes with processing conditions. The through-plane exceeded the in-plane thermal conductivity for all energy densities. A co-located thermal conductivity map by frequency domain thermoreflectance (FDTR) and crystallographic grain orientation map by electron backscattered diffraction (EBSD) was used to investigate the effect of microstructure on thermal conductivity. Findings The highest through-plane thermal conductivity (136 ± 2 W/m-K) was achieved at 59 J/mm 3 and exceeded the values reported previously. The in-plane thermal conductivity peaked at 117 ± 2 W/m-K at 50 J/mm 3 . The trend of thermal conductivity reducing with energy density at similar porosity was primarily due to the reduced grain size producing more Al-Si interfaces that pose thermal resistance. At these interfaces, thermal energy must convert from electrons in the aluminum to phonons in the silicon. The co-located thermal conductivity and crystallographic grain orientation maps confirmed that larger colonies of columnar grains have higher thermal conductivity compared to smaller columnar grains. Practical implications The thermal properties of AlSi10Mg are crucial to heat transfer applications including additively manufactured heatsinks, cold plates, vapor chambers, heat pipes, enclosures and heat exchangers. Additionally, thermal-based nondestructive testing methods require these properties for applications such as defect detection and simulation of L-PBF processes. Industrial standards for L-PBF processes and components can use the data for thermal applications. Originality/value To the best of the authors’ knowledge, this paper is the first to make coupled thermal conductivity maps that were matched to microstructure for L-PBF AlSi10Mg aluminum alloy. This was achieved by a unique in-house thermal conductivity mapping setup and relating the data to local SEM EBSD maps. This provides the first conclusive proof that larger grain sizes can achieve higher thermal conductivity for this processing method and material system. This study also shows that control of the solidification can result in higher thermal conductivity. It was also the first to find that the build substrate (with or without support) has a large effect on thermal conductivity. 

We demonstrate a process to selective laser melt a metal alloy directly onto graphite. The heat trans- fer applications of metal features printed onto annealed pyrolytic graphite are compelling, as pyrolytic graphite has the second highest in-plane thermal conductivity ( > 1500 W/m-K at room temperature) of any bulk material. While the bonding of metal alloys commonly used in selective laser melting (SLM) with graphite is relatively weak, the proper interlayer material drastically improves the wetting and bond- ing. The challenge is the alloys that typically bond to graphite require extended bonding times at elevated temperatures (minutes to hours), while the SLM process delivers only brief exposures to high tempera- tures ( ∼100 μs). In this paper, we employ a Sn3Ag4Ti alloy that rapidly forms a nanometer-thin layer of TiC, as verified by transmission electron microscopy. The influence of graphite thermal properties on interfacial bond strength is shown by mechanical testing and simulations of selective laser melting. 

Surface segregation is a phenomenon that depends on the delicate interplay between thermodynamic driving forces and kinetic obstacles, for which elevated temperature is often needed to enhance the atom mobility and reach equilibrium. Using the classic system of Cu3Au(100) under the non-isothermal conditions, herein we show an adatom process underlying transient surface segregation dynamics through the temperaturechange-driven creation and annihilation of thermal vacancies in the bulk and the resulting bulk/surface mass exchanges. This is demonstrated by monitoring the surface composition evolution of Cu3Au(100) with temperature changes between 250 °C and 500 °C, showing that the increase in temperature decreases monotonically the surface Au concentration as a result of the transfer of more Cu than Au from the bulk to the surface to form Cu-rich clusters of adatoms. Such a bulk thermal defect effect is expected to be universal in inducing the disparity in the bulk/surface mass exchanges of dissimilar atoms in multicomponent materials because of the inherent differences in the vacancy formation energies of the constituent atoms.