Metastable hexagonal close-packed palladium hydride in liquid cell TEM.

Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.

Corrosion Properties of Ultra-Fine-Grained Cu-3 wt%Ti Alloy Fabricated by Combination of Hot Rolling and Aging Treatment.

Although deformation and aging treatments of Cu-3 wt%Ti alloys dramatically enhance their mechanical properties, the corrosion behavior of ultra-fine grained (UFG) Cu-3 wt%Ti alloys produced by a combination of hot rolling and artificial aging has not been extensively explored yet. To bridge this gap, we herein probe the corrosion behavior of an UFG Cu-3 wt%Ti alloy produced by cold rolling and artificial aging, revealing that cast sample corrosion preferentially occurs around the ß-Cu4Ti phase. Compared to that of the coarse-grained Cu-3 wt%Ti alloy, the corrosion resistance of its UFG counterpart is remarkably higher, which is ascribed to the effects of grain refinement and enveloping between the α-Cu matrix and ß-Cu4Ti in the absence of pitting corrosion. The development of ultra-fine microstructure upon the introduction of severe deformation is shown to dramatically improve the corrosion resistance of aging-hardened Cu-3 wt%Ti alloys without sacrificing their mechanical properties. Finally, we demonstrate that solid solution treatment of the Cu-3 wt%Ti alloy results in serious mechanical property deterioration, even though the thus treated samples feature the lowest corrosion current density.

Microstructural Evolution and Electrochemical Properties of HRDSR AZ61-X (X = Ca, Ti) Alloys.

The microstructure and corrosion properties of as-cast AZ61 (Mg-6%Al-1%Zn) and AZ61 alloys doped with titanium and calcium and subjected to high ratio differential speed rolling were investigated. Addition of the alloying elements to the AZ61 alloy resulted in remarkable modification of the morphology and the amount of continuous ß (Mg17Al12)-phase. Addition of Ti to the as-cast AZ61 alloy causes a decrease in the volume fraction (or discontinuity of the ß-phase), leading to strong anodic dissolution. In contrast, addition of Ca to the as-cast AZ61 alloy is rather effective for preventing pitting corrosion. This is attributed to the formation of a semi-continuous network ß-structure. The (Mg, Al)4Ca phases dispersed between the ß (Mg17Al12)-phases led to continuity in the AZ61 alloy with Ca. The AZ61 and AZ61-X(Ca, Ti) alloys subjected to severe plastic deformation via high-ratio differential speed rolling possessed a nano-composite-like microstructure in which the α-Mg matrix with an ultra-fine grain was surrounded by a large number of fine ß particles. These particles were either dynamically precipitated or broken at the grain boundaries, as well as in the grain interiors, by the high ratio differential speed rolling process. The corrosion resistance of the AZ61 and AZ61-X (X = Ca, Ti) alloys subjected to high ratio differential speed rolling was largely improved by the microstructural modification. The high ratio differential speed rolling process greatly influenced the texture of the Mg alloys, which significantly affected their corrosion behavior.

Microstructural analysis of dehydrogenation products of the Ca(BH4)2-MgH2 composite.

The microstructural analysis of the dehydrogenation products of the Ca(BH4)2-MgH2 composite was performed using transmission electron microscopy. It was found that nanocrystalline CaB6 crystallites formed as a dehydrogenation product throughout the areas where the signals of Ca and Mg were simultaneously detected, in addition to relatively coarse Mg crystallites. The uniform distribution of the nanocrystalline CaB6 crystallites appears to play a key role in the rehydrogenation of the dehydrogenation products, which implies that microstructure is a crucial factor determining the reversibility of reactive hydride composites.

Nanoscale light element identification using machine learning aided STEM-EDS.

Light element identification is necessary in materials research to obtain detailed insight into various material properties. However, reported techniques, such as scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectroscopy (EDS) have inadequate detection limits, which impairs identification. In this study, we achieved light element identification with nanoscale spatial resolution in a multi-component metal alloy through unsupervised machine learning algorithms of singular value decomposition (SVD) and independent component analysis (ICA). Improvement of the signal-to-noise ratio (SNR) in the STEM-EDS spectrum images was achieved by combining SVD and ICA, leading to the identification of a nanoscale N-depleted region that was not observed in as-measured STEM-EDS. Additionally, the formation of the nanoscale N-depleted region was validated using STEM-electron energy loss spectroscopy and multicomponent diffusional transformation simulation. The enhancement of SNR in STEM-EDS spectrum images by machine learning algorithms can provide an efficient, economical chemical analysis method to identify light elements at the nanoscale.

Microstructure and properties of silicon-incorporated DLC film fabricated using HMDS gas and RF-PECVD process.

The microstructure and characteristics of silicon-incorporated diamond-like carbon film, fabricated using a radio-frequency plasma-enhanced chemical vapor deposition process with hexamethyldisilane [(CH3)3,Si x Si(CH3)3:HMDS] gas as a silicon source, were investigated. Diamond-like carbon films with silicon compositions from 0 to 5 atomic percent were deposited onto ultra-fine grained AZ31 magnesium alloy substrate as buffer layers or multilayers. Si doping led not only to an increase in the bonding ratio (sp3/sp2), but improvements in hardness, critical adhesion, and corrosion resistance. Out of the investigated samples, the multi-deposited silicon diamond-like carbon thin film on magnesium substrate showed the best combination of adhesive, wear resistance, and corrosion resistance properties.