Fast Grain Mapping with Sub-Nanometer Resolution Using 4D-STEM with Grain Classification by Principal Component Analysis and Non-Negative Matrix Factorization

High-throughput grain mapping with sub-nanometer spatial resolution is demonstrated using scanning nanobeam electron diffraction (also known as 4D scanning transmission electron microscopy, or 4D-STEM) combined with high-speed direct electron detection. An electron probe size down to 0.5 nm in diameter is implemented and the sample investigated is a gold-palladium nanoparticle catalyst. Computational analysis of the 4D-STEM data sets is performed using a disk registration algorithm to identify the diffraction peaks followed by feature learning to map the individual grains. Two unsupervised feature learning techniques are compared: Principal component analysis (PCA) and non-negative matrix factorization (NNMF). The characteristics of the PCA versus NNMF output are compared and the potential of the 4D-STEM approach for statistical analysis of grain orientations at high spatial resolution is discussed

Growth Mechanism and Electronic Structure of Zn_3P_2 on the Ga-Rich GaAs(001) Surface

The growth of epitaxial Zn_3P_2 films on III–V substrates unlocks a promising pathway toward high-efficiency, earth-abundant photovoltaic devices fabricated on reusable, single-crystal templates. The detailed chemical, structural, and electronic properties of the surface and interface of pseudomorphic Zn_3P_2 epilayers grown on GaAs(001) were investigated using scanning tunneling microscopy/spectroscopy and high-resolution X-ray photoelectron spectroscopy. Two interesting features of the growth process were observed: (1) vapor-phase P4 first reacts with the Ga-rich GaAs surface to form an interfacial GaP layer with a thickness of several monolayers, and (2) a P-rich amorphous overlayer is present during the entire film growth process, beneath which a highly ordered Zn_3P_2 crystalline phase is precipitated. These features were corroborated by transmission electron micrographs of the Zn_3P_2/GaAs interface as well as density functional theory calculations of P reactions with the GaAs surface. Finally, the valence-band offset between the crystalline Zn_3P_2 epilayer and the GaAs substrate was determined to be ΔE_V = 1.0 ± 0.1 eV, indicating the formation of a hole-depletion layer at the substrate surface which may inhibit formation of an ohmic contact

Imaging 3D Chemistry at 1 nm Resolution with Fused Multi-Modal Electron Tomography

Measuring the three-dimensional (3D) distribution of chemistry in nanoscale matter is a longstanding challenge for metrological science. The inelastic scattering events required for 3D chemical imaging are too rare, requiring high beam exposure that destroys the specimen before an experiment completes. Even larger doses are required to achieve high resolution. Thus, chemical mapping in 3D has been unachievable except at lower resolution with the most radiation-hard materials. Here, high-resolution 3D chemical imaging is achieved near or below one nanometer resolution in a Au-Fe$_3$O$_4$ metamaterial, Co$_3$O$_4$ - Mn$_3$O$_4$ core-shell nanocrystals, and ZnS-Cu$_{0.64}$S$_{0.36}$ nanomaterial using fused multi-modal electron tomography. Multi-modal data fusion enables high-resolution chemical tomography often with 99\% less dose by linking information encoded within both elastic (HAADF) and inelastic (EDX / EELS) signals. Now sub-nanometer 3D resolution of chemistry is measurable for a broad class of geometrically and compositionally complex materials

MOF-Derived RuCo Catalyzes the Formation of a Plasticizer Alcohol from Renewable Precursors

The Guerbet reaction can be used for the condensation of simple bioalcohols, which simultaneously doubles the carbon count and increases the C:O ratio, to yield valuable commodity chemicals. Here, we report a metal–organic framework (MOF)-derived RuCo catalyst that furnishes 2-ethylhexanol, a plasticizer alcohol currently produced on a 2 Mt/a scale. While the industrial route requires propene, the MOF-derived catalyst uses 1-butanol and delivers turnover numbers up to 1.7 × 106 Ru–1. In combination with K3PO4, it serves as a fully heterogeneous catalyst system that yields the Guerbet alcohol without producing sodium butanoate, a common secondary product from the undesired Cannizzaro reaction

Mobile evaporator corrosion test results

Laboratory corrosion tests were conducted on eight candidates to select a durable and cost-effective alloy for use in mobile evaporators to process radioactive waste solutions. Based on an extensive literature survey of corrosion data, three stainless steel alloys (304L, 316L, AL-6XN), four nickel-based alloys (825, 625, 690, G-30), and titanium were selected for testing. The corrosion tests included vapor phase, liquid junction (interface), liquid immersion, and crevice corrosion tests on plain and welded samples of candidate materials. Tests were conducted at 80{degrees}C for 45 days in two different test solutions: a nitric acid solution. to simulate evaporator conditions during the processing of the cesium ion-exchange eluant and a highly alkaline sodium hydroxide solution to simulate the composition of Tank 241-AW-101 during evaporation. All of the alloys exhibited excellent corrosion resistance in the alkaline test solution. Corrosion rates were very low and localized corrosion was not observed. Results from the nitric acid tests showed that only 316L stainless steel did not meet our performance criteria. The 316L welded interface and crevice specimens had rates of 22.2 mpy and 21.8 mpy, respectively, which exceeds the maximum corrosion rate of 20 mpy. The other welded samples had about the same corrosion resistance as the plain samples. None of the welded samples showed preferential weld or heat-affected zone (HAZ) attack. Vapor corrosion was negligible for all alloys. All of the alloys except 316L exhibited either {open_quotes}satisfactory{close_quotes} (2-20 mpy) or {open_quotes}excellent{close_quotes} (<2 mpy) corrosion resistance as defined by National Association of Corrosion Engineers. However, many of the alloys experienced intergranular corrosion in the nitric acid test solution, which could indicate a susceptibility to stress corrosion cracking (SCC) in this environment