Size-Dependent Corrosion of Al-Fe Intermetallic Particles at Al-Mg Alloy Surfaces Investigated by In-Liquid Nanoscale Potential Measurement Technique.

Corrosion of Al alloy often starts from the nanoscale corrosion around the surface-exposed Al-Fe intermetallic particles (IMPs) and leads to a serious damage limiting its application range in the automobile industry. To solve this issue, understanding of the nanoscale corrosion mechanism around the IMP is essential, yet it is impeded by the difficulties in directly visualizing nanoscale distribution of reaction activity. Here, this difficulty is overcomed by open-loop electric potential microscopy (OL-EPM) and investigate nanoscale corrosion behavior around the IMPs in H2 SO4 solution. The OL-EPM results reveal that the corrosion around a small IMP settles down in a short time (<30 min) after transient dissolution of the IMP surface while that around a large IMP lasts for a long time especially at its edges and results in a severe damage of the IMP and matrix. This result suggests that an Al alloy with many small IMPs gives a better corrosion resistance than that with few large IMPs if the total Fe content is the same. This difference is confirmed by corrosion weight loss test using Al alloys with different IMP sizes. This finding should give an important guideline to improve the corrosion resistance of Al alloy.

Surface Effect on Young's Modulus of Sub-Two-Nanometer Gold [111] Nanocontacts.

The surface bond nature of face centered cubic metals has been controversial between hardening and softening theoretically because of the lack of precise measurement. Here, we precisely measured the size dependence of Young's modulus of gold [111] nanocontacts with a clean surface by our in situ TEM-frequency modulation force sensing method in ultrahigh vacuum at room temperature. Young's modulus gradually decreased from ca. 80 to 30 GPa, as the nanocontact width decreased below 2 nm, which could be explained by surface softening; Young's modulus of the outermost atomic layer was estimated to be approximately 22 GPa, while that of the other part was almost the same with the bulk.

Peculiar Atomic Bond Nature in Platinum Monatomic Chains.

Metal atomic chains have been reported to change their electronic or magnetic properties by slight mechanical stimulus. However, the mechanical response has been veiled because of lack of information on the bond nature. Here, we clarify the bond nature in platinum (Pt) monatomic chains by our in situ transmission electron microscope method. The stiffness is measured with sub-N/m precision by quartz length-extension resonator. The bond stiffnesses at the middle of the chain and at the connection to the base are estimated to be 25 and 23 N/m, respectively, which are higher than the bulk counterpart. Interestingly, the bond length of 0.25 nm is found to be elastically stretched to 0.31 nm, corresponding to a 24% strain. Such peculiar bond nature could be explained by a novel concept of "string tension". This study is a milestone that will significantly change the way we think about atomic bonds in one-dimension.

Atomic scale mechanics explored by in situ transmission electron microscopy with a quartz length-extension resonator as a force sensor.

An in situ transmission electron microscopy (TEM) holder equipped with a quartz length-extension resonator (LER) as a force sensor was developed to examine the elastic properties of atomic-scale materials. This holder is a useful means of studying the effects of size and crystal orientation on the properties of nanomaterials via measurements of mechanical responses while simultaneously observing atomic structures. The spring constants of nanocontacts (NCs) were determined based on shifts in the resonance frequency of the LER during TEM observations. The LER spring constant and sensitivity (the ratio of the LER induced charge to its oscillation amplitude), both of which are crucial to mechanical evaluation of NCs, were precisely calibrated from an analysis of TEM images along with the output of the electronics attached to the holder. The mechanical stability of the newly developed TEM holder was sufficient to allow chains of Pt atoms in the NC to be maintained for at least several seconds. The minimum measurable NC spring constant was on the order of 1 N m-1, comparable to that associated with a single atomic bond. The spring constant of a NC composed of a single-bonded chain of two Pt atoms was found to be 13.2 N m-1. This holder therefore has significant potential with regard to the characterization of nanoscale mechanical properties.

Two-Dimensional, Hierarchical Ag-Doped TiO2 Nanocatalysts: Effect of the Metal Oxidation State on the Photocatalytic Properties.

This paper reports the synthesis of two-dimensional, hierarchical, porous, and (001)-faceted metal (Ag, Zn, and Al)-doped TiO2 nanostructures (TNSs) and the study of their photocatalytic activity. Two-dimensional metal-doped TNSs were synthesized using the hydrolysis of ammonium hexafluorotitanate in the presence of hexamethylenetetramine and metal precursors. Typical morphology of metal-doped TNSs is a hierarchical nanosheet that is composed of randomly stacked nanocubes (dimensions of up to 5 µm and 200 nm in edge length and thickness, respectively) and has dominant (001) facets exposed. Raman analysis and X-ray photoelectron spectroscopy results indicated that the Ag doping, compared to Zn and Al, much improves the crystallinity degree and at the same time dramatically lowers the valence state binding energy of the TNS and provides an additional dopant oxidation state into the system for an enhanced electron-transfer process and surface reaction. These are assumed to enhance the photocatalytic of the TNS. In a model of photocatalytic reaction, that is, rhodamine B degradation, the AgTNS demonstrates a high photocatalytic activity by converting approximately 91% of rhodamine B within only 120 min, equivalent to a rate constant of 0.018 m-1 and ToN and ToF of 94 and 1.57 min-1, respectively, or 91.1 mmol mg-1 W-1 degradation when normalized to used light source intensity, which is approximately 2 times higher than the pristine TNS and several order higher when compared to Zn- and Al-doped TNSs. Improvement of the crystallinity degree, decrease in the defect density and the photogenerated electron and hole recombination, and increase of the oxygen vacancy in the AgTNS are found to be the key factors for the enhancement of the photocatalytic properties. This work provides a straightforward strategy for the preparation of high-energy (001) faceted, two-dimensional, hierarchical, and porous Ag-doped TNSs for potential use in photocatalysis and photoelectrochemical application.

Hierarchical Bimetallic AgPt Nanoferns as High-Performance Catalysts for Selective Acetone Hydrogenation to Isopropanol.

A combinative effect of two or more individual material properties, such as lattice parameters and chemical properties, has been well-known to generate novel nanomaterials with special crystal growth behavior and physico-chemical performance. This paper reports unusually high catalytic performance of AgPt nanoferns in the hydrogenation reaction of acetone conversion to isopropanol, which is several orders higher compared to the performance shown by pristine Pt nanocatalysts or other metals and metal-metal oxide hybrid catalyst systems. It has been demonstrated that the combinative effect during the bimetallisation of Ag and Pt produced nanostructures with a highly anisotropic morphology, i.e., hierarchical nanofern structures, which provide high-density active sites on the catalyst surface for an efficient catalytic reaction. The extent of the effect of structural growth on the catalytic performance of hierarchical AgPt nanoferns is discussed.

Quasi-stabilized hydration layers on muscovite mica under a thin water film grown from humid air.

The interfaces between solids and water films in air play fundamental roles in physicochemical phenomena, biological functions, and nano-fabrication. Though the properties of the interfaces have been considered to be irrelevant to the water film thickness, we found distinctive mechanical features of the interface between a cleaved muscovite mica surface and a thin water film grown in humid air, dissimilar to those in bulk water, using frequency-modulation atomic force microscopy. The thin water film grew with quasi-stabilized hydration networks of water molecules, tightly bound each other at the interface, to a thickness of ~2 nm at near-saturating humidity. Consequently, defective structures of the hydration networks persisted vertically through the hydration layers at the interface, and K+ ions on the cleaved surface remained without dissolution into the water film. The results provide atomistic insights into thin water films in regard to epitaxial-like growth from vapour and the motion of water molecules and ions therein.

Evaluation and optimization of quartz resonant-frequency retuned fork force sensors with high Q factors, and the associated electric circuits, for non-contact atomic force microscopy.

High-Q factor retuned fork (RTF) force sensors made from quartz tuning forks, and the electric circuits for the sensors, were evaluated and optimized to improve the performance of non-contact atomic force microscopy (nc-AFM) performed under ultrahigh vacuum (UHV) conditions. To exploit the high Q factor of the RTF sensor, the oscillation of the RTF sensor was excited at its resonant frequency, using a stray capacitance compensation circuit to cancel the excitation signal leaked through the stray capacitor of the sensor. To improve the signal-to-noise (S/N) ratio in the detected signal, a small capacitor was inserted before the input of an operational (OP) amplifier placed in an UHV chamber, which reduced the output noise from the amplifier. A low-noise, wideband OP amplifier produced a superior S/N ratio, compared with a precision OP amplifier. The thermal vibrational density spectra of the RTF sensors were evaluated using the circuit. The RTF sensor with an effective spring constant value as low as 1000 N/m provided a lower minimum detection limit for force differentiation. A nc-AFM image of a Si(111)-7 × 7 surface was produced with atomic resolution using the RTF sensor in a constant frequency shift mode; tunneling current and energy dissipation images with atomic resolution were also simultaneously produced. The high-Q factor RTF sensor showed potential for the high sensitivity of energy dissipation as small as 1 meV/cycle and the high-resolution analysis of non-conservative force interactions.

Atom-resolved analysis of an ionic KBr(001) crystal surface covered with a thin water layer by frequency modulation atomic force microscopy.

An ionic KBr(001) crystal surface covered with a thin water layer was observed with a frequency modulation atomic force microscope (FM-AFM) with atomic resolution. By immersing only the tip apex of the AFM cantilever in the thin water layer, the Q-factor of the cantilever in probing the solid-liquid interface can be maintained as high as that of FM-AFM operation in air, leading to improvement of the minimum detection of a differential force determined by the noise. Two types of images with atom-resolved contrast were observed, possibly owing to the different types of ions (K(+) or Br(-)) adsorbed on the tip apex that incorporated into the hydration layers on the tip and on the sample surface. The force-distance characteristics at the solid-water interface were analyzed by taking spatial variation maps of the resonant frequency shift of the AFM cantilever with the high Q-factor. The oscillatory frequency shift-distance curves exhibited atomic site dependence. The roles of hydration and the ions on the tip and on the sample surface in the measurements were discussed.

Microscopic techniques bridging between nanoscale and microscale with an atomically sharpened tip - field ion microscopy/scanning probe microscopy/ scanning electron microscopy.

Over a hundred years an atomistic point of view has been indispensable to explore fascinating properties of various materials and to develop novel functional materials. High-resolution microscopies, rapidly developed during the period, have taken central roles in promoting materials science and related techniques to observe and analyze the materials. As microscopies with the capability of atom-imaging, field ion microscopy (FIM), scanning tunneling microscopy (STM), atomic force microscopy (AFM) and transmission electron microscopy (TEM) can be cited, which have been highly evaluated as methods to ultimately bring forward the viewpoint of reductionism in materials science. On one hand, there have been difficulties to derive useful and practical information on large (micro) scale unique properties of materials using these excellent microscopies and to directly advance the engineering for practical materials. To make bridges over the gap between an atomic scale and an industrial engineering scale, we have to develop emergence science step-by-step as a discipline having hierarchical structures for future prospects by combining nanoscale and microscale techniques; as promising ways, the combined microscopic instruments covering the scale gap and the extremely sophisticated methods for sample preparation seem to be required. In addition, it is noted that spectroscopic and theoretical methods should implement the emergence science.Fundamentally, the function of microscope is to determine the spatial positions of a finite piece of material, that is, ultimately individual atoms, at an extremely high resolution with a high stability. To define and control the atomic positions, the STM and AFM as scanning probe microscopy (SPM) have successfully demonstrated their power; the technological heart of SPM lies in an atomically sharpened tip, which can be observed by FIM and TEM. For emergence science we would like to set sail using the tip as a base. Meanwhile, it is significant to extend a model sample prepared for the microscopies towards a microscale sample while keeping the intrinsic properties found by the microscopies.In this study we present our trial of developing microscopic combined instruments among FIM, field emission microscopy (FEM), STM, AFM and scanning electron microscopy (SEM), in which we prepared and characterized the tips for the SPM, and in addition, the sample preparation to take a correlation between nanoscale and microscale properties of functional materials. Recently, we developed a simple sample preparation method of a rutile single crystal TiO2 covered with an epitaxially-grown monolayer of SiO2 by annealing the crystals in a furnace at high temperatures in air; the crystal samples were placed into a quartz container in the furnace [1]. The vapor of SiO evaporated from the quartz container were adsorbed on the crystal while the crystal surfaces being fully oxidized in air. The SiO2-TiO2 composite systems are promising to protect catalytic TiO2 performance; the photo-catalytic activity is kept by coating with hard and stable SiO2 layers and to extend the lifetime of water super-hydrophilicity even in dark, though understanding of their properties is insufficient due to the lack of techniques to fabricate a well-characterized system on a nanoscale to conduct control experiments. The SiO2 overlayers were observed by low energy electron diffraction (LEED) in vacuum and frequency-modulation (FM) AFM in water [1,2], and water contact angles (WCA) were measured [2]. Although the WCA measurement seems a classic characterization, this method possesses a high potential to make a bridge by controlling the environmental conditions. We will discuss the details.

Interplay between nonlinearity, scan speed, damping, and electronics in frequency modulation atomic-force microscopy.

Numerical simulations of the frequency modulation atomic force microscope, including the whole dynamical regulation by the electronics, show that the cantilever dynamics is conditionally stable and that there is a direct link between the frequency shift and the conservative tip-sample interaction. However, a soft coupling between the electronics and the nonlinearity of the interaction may significantly affect the damping. A resonance between the scan speed and the response time of the system can provide a simple explanation for the spatial shift and contrast inversion between topographical and damping images, and for the extreme sensitivity of the damping to a tip change.