HREM image contrast from supported small metal particles

HREM, image calculations and small probe diffraction/AEM have been used to characterize structure and contrast of supported small metal particles of ≤5 nm diameter. Such small particles are thought to be active species in industrial applications such as in heterogeneous catalysis where, in general, the particles employed as catalysts are supported. Image calculations (HREM and diffraction contrast) carried out at both 200 keV and 400 keV at various defoci and support thicknesses have shown that in HREM, particle images are obscured by the support contrast with the loss of edge definition and particles appear to be smaller than they actually are. The particle visibility is better at 400 keV. The calculations have also indicated that particle shape varies as a function of support thickness and defocus. The results have clear implications for identification and interpretation of surface structure of the supported small particles accurately by HREM if not performed under controlled conditions and for determining their size and shape.     

What atomic resolution annular dark field imaging can tell us about gold nanoparticles on (1 1 0)

Annular dark field scanning transmission electron microscopy imaging was recently applied to a catalyst consisting of gold nanoparticles on TiO₂ (1 1 0), showing directly that the gold atoms in small nanoparticles preferentially attach to specific sites on the TiO₂ (1 1 0) surface. Here, through simulation, a parameter exploration of the imaging conditions which maximise the visibility of such nanoparticles is presented. Aberration correction, finite source size and profile imaging are all considered while trying to extracting the maximum amount of information from a given sample. Comment is made on the role of the thermal vibration of the atoms in the nanoparticle, the magnitude of which is generally not known a priori but which affects the visibility of the nanoparticles in this imaging mode.     

Contrast analysis of cryo-images of n-paraffin recorded at 400***kV out to 2·1 Å resolution

N-Paraffin was used as a test specimen for evaluating the relative merits of 400-kV versus 100-kV electron microscopy in recording data for electron crystallographic analysis of beam-sensitive materials. The parameter used for comparison, the relative contrast R, is the ratio of amplitudes from the computed Fourier transform of images and amplitudes from an electron diffraction pattern from the same crystal. R will thus be a measure of the contrast from an experimental image relative to that of a perfect image. Electron diffraction patterns and bright-field images were recorded at 400 kV at a specimen temperature of ?167°C. Using the flood-beam imaging technique the best R-value is 0 08 for all reflections in the resolution zone from 4 to 3 Å. This value is equivalent to that found at 100 kV. In the resolution zone from 3 to 2 Å we have found R — 0 02. Using the spot-scan imaging technique, on the other hand, R was measured to be 0·42 for the reflections between 4- and 3-Å resolution. This amount of relative contrast is 1·7 times that observed at 100 kV. Reflections at 3–2 Å displayed an R-value of 0 05. Besides obtaining higher R-values when applying the spot-scan imaging technique at 400 kV, we observe a higher yield of images with isotropic diffraction and/or higher resolution reflections. Various contrast-attenuating factors, including the modulation transfer function of the photographic film and the cryo-holder, envelope functions for spatial and temporal coherence and lens and high-tension instabilities, the contrast transfer function and lastly the radiation damage effects, have been considered in interpreting the observed image contrast. Overall, use of 400 kV in combination with spot-scan does offer important improvements in contrast levels, which can be very useful in determining the three-dimensional structure from protein crystals.     

Revealing local variations in nanoparticle size distributions in supported catalysts: a generic TEM specimen preparation method

The specimen preparation method is crucial for how much information can be gained from transmission electron microscopy (TEM) studies of supported nanoparticle catalysts. The aim of this work is to develop a method that allows for observation of size and location of nanoparticles deposited on a porous oxide support material. A bimetallic Pt‐Pd/Al₂O₃ catalyst in powder form was embedded in acrylic resin and lift‐out specimens were extracted using combined focused ion beam/scanning electron microscopy (FIB/SEM). These specimens allow for a cross‐section view across individual oxide support particles, including the unaltered near surface region of these particles. A site‐dependent size distribution of Pt‐Pd nanoparticles was revealed along the radial direction of the support particles by scanning transmission electron microscopy (STEM) imaging. The developed specimen preparation method enables obtaining information about the spatial distribution of nanoparticles in complex support structures which commonly is a challenge in heterogeneous catalysis.     

Recent advances and applications of high resolution electron microscopy

This review covers several broad areas: firstly, recent developments in HREM instrumentation, and then novel techniques for imaging are discussed, including some of the problems of image interpretation. Applications of HREM techniques to a wide range of materials problems are described and include solid state chemistry, ceramics, semiconductors, metals and natural diamonds. The next generation of high resolution microscopes will operate in the 300–400 kV range, have low C_s objective lenses, and have sufficiently good vacuum to allow the combined use of CBED and EELS facilities with imaging in the sub-2 Å range. Microprocessor control of instrumental parameters such as astigmatism, alignment and defocus are seen as an important way forward in achieving the optimum performance of these instruments.     

Catalyst particle sizes from Rutherford scattered intensities

We show that the number of atoms in a small supported catalyst cluster can be estimated from the strength of electron scattering into a high angle annular detector in the STEM. The technique is related to the Z contrast methods developed by Crewe, Wall, Langmore and Isaacson. It works best for high atomic number catalyst particles when supported on low atomic number supports, such as Pt on γ-aluminium oxide. The method is particularly useful for detecting and measuring particles in the sub-nanometre size range where bright field images are unreliable. Unlike the Z contrast methods, a high angle annular detector is used, which avoids intensity modulations arising from Bragg reflections. The signal is mostly high angle diffuse scattering, which is predominantly Rutherford scattering, and is proportional to the number of atoms probed by the beam, weighted by their individual scattering cross-sections. Scattering strengths of individual clusters are computed from digitized high angle annular detector images. Data for Pt on γ-aluminium oxide, when plotted as imaged area^1/2 against intensity^1/3, define a straight line. Such plots provide calibration of the intensity increment per atom without the need of external calibration, although assumptions about particle morphology must be made. Reliable results require high signal-to-noise and optimum sampling of the specimen. For an STEM probe size of 0.35 nm, Pt clusters containing as few as three atoms can be detected when supported on typical, 20 nm thick, γ-aluminium oxide supports.     

Supported metal model catalyst surfaces examined by scanning tunnelling microscopy

Topographic and/or barrier-height images of ultrafine Pt and Au metal particles supported on a vacuum-deposited carbon film or titanium oxide thin films grown on titanium metal sheets were obtained. The topographic images of colloidal Au particles (5-nm diameter) adsorbed on a titanium oxide thin film showed a structure elongated in the direction normal to the x scan, indicating their weak interaction with the support surface. The topographic images of Pt vacuum-deposited on a carbon film showed c. 4-nm diameter particles, larger than those observed in electron microscopy. The problems inherent to the STM observation of such dispersed metal systems are identified. In the case of Pt particles vacuum-deposited on titanium oxide film, its barrier-height image gave better indication of different phases on the surface than its topographic image. The significance of obtaining barrier-height images along with topographic images for such sample systems is demonstrated.     

Specimen preparation technique for high resolution transmission electron microscopy studies on model supported metal catalysts

A new technique is described which can be used for preparing transmission electron microscopy (TEM) specimens suitable for high resolution studies on supported metal catalysts. By conventional silicon processing techniques 200 × 200 μm² Si₃N₄ membranes on Si wafers are produced. These membranes are extremely flat and have a uniform thickness of 13 nm. They can be used as a support in various kinds of thin film deposition. A TiO₂ film, optimally structured with respect to the requirements for high resolution TEM work in TiO₂–metal cluster systems, is deposited on the Si₃N₄ layer. It consists of one monolayer of 10–25 nm TiO₂ crystallites. TiO₂ lattice images show that a line resolution down to 0.19 nm is possible. Examples of TiO₂–Pd and TiO₂–Rh are given using respectively photodeposition and impregnation reduction to produce l.5–4 nm metal clusters.     

Process optimization and material properties for nanofluid manufacturing

Using an innovative nanofluid preparation method, ultrasonic-aidedsubmerged arc nanoparticle synthesis system, this paper employs the robustness design method to examine the optimal parameters, such as peak current, pulse duration, open voltage and amplitude of ultrasonic vibration, for obtaining the optimal process for TiO₂ nanofluid preparation. Experimental results show that the proposed manufacturing system can successfully prepare uniformly distributed TiO₂ nanoparticle using the optimal parameters. The pH of the as prepared TiO₂ nanofluid is 7.5, which is much higher than that of isoelectric point, about 4.4. Hence, the suspended TiO₂ nanoparticles already possess electrostatic stability properties. Regarding ultraviolet/visible absorbency, the produced TiO₂ nanofluid would absorb UV energy when the wavelength is 280 nm to 400 nm. According to the UV-Vis absorption spectrum analysis, the energy band gap of the prepared TiO₂ nanoparticle is 3.4 eV.     

Real‐space observation of strong metal‐support interaction: state‐of‐the‐art and what's the next

The real‐space resolving of the encapsulated overlayer in the well‐known model and industry catalysts, ascribed to the advent of dedicated transmission electron microscopy, enables us to probe novel nano/micro architecture chemistry for better application, revisiting our understanding of this key issue in heterogeneous catalysis. In this review, we summarize the latest progress of real‐space observation of SMSI in several well‐known systems mainly covered from the metal catalysts (mostly Pt) supported by the TiO₂, CeO₂ and Fe₃O₄. As a comparison with the model catalyst Pt/Fe₃O₄, the industrial catalyst Cu/ZnO is also listed, followed with the suggested ongoing directions in the field.     

A high-performance source of high-power nanosecond ultrawideband radiation pulses

A source of high-power nanosecond ultrawideband electromagnetic pulses is described. The 3-ns-long bipolar voltage pulse with a 90-kV amplitude is applied to the input of four-element antenna array. The effective radiation potential values E _p R = 560 kV were obtained at a 100-Hz pulse repetition rate.     

Transmission electron microscopy at 20 kV for imaging and spectroscopy

The electron optical performance of a transmission electron microscope (TEM) is characterized for direct spatial imaging and spectroscopy using electrons with energies as low as 20 keV. The highly stable instrument is equipped with an electrostatic monochromator and a C_S-corrector. At 20 kV it shows high image contrast even for single-layer graphene with a lattice transfer of 213 pm (tilted illumination). For 4 nm thick Si, the 200 reflections (271.5 pm) were directly transferred (axial illumination). We show at 20 kV that radiation-sensitive fullerenes (C₆₀) within a carbon nanotube container withstand an about two orders of magnitude higher electron dose than at 80 kV. In spectroscopy mode, the monochromated low-energy electron beam enables the acquisition of EELS spectra up to very high energy losses with exceptionally low background noise. Using Si and Ge, we show that 20 kV TEM allows the determination of dielectric properties and narrow band gaps, which were not accessible by TEM so far. These very first results demonstrate that low kV TEM is an exciting new tool for determination of structural and electronic properties of different types of nano-materials.     

High-resolution rlectron microscopic investigation of supported platinum particles reduced at high temperatures

High-resolution electron microscopy has been used to characterize the platinum particles supported on TiO₂ or ZnO. After reduction at elevated temperatures, the metallic particles display a regular, faceted shape, and several superstructures, Pt₃ Ti(C), Pt₃ Ti(H), PtTi, and PtZn, have been found. These results, which may involve strong metal-support interaction, have been confirmed by optical diffraction and image simulation.     

Low-voltage electron microscopy of polymer and organic molecular thin films

We have demonstrated the capabilities of a novel low-voltage electron microscope (LVEM) for imaging polymer and organic molecular thin films. The LVEM can operate in transmission electron microscopy, scanning transmission electron microscopy, scanning electron microscopy, and electron diffraction modes. The microscope operates at a nominal accelerating voltage of 5 kV and fits on a tabletop. A detailed discussion of the electron-sample interaction processes is presented, and the mean free path for total electron scattering was calculated to be 15 nm for organic samples at 5 kV. The total end point dose for the destruction of crystallinity at 5 kV was estimated at 5 x 10(-4) and 3.5 x 10(-2) C/cm2 for polyethylene and pentacene, respectively. These values are significantly lower than those measured at voltages greater than 100 kV. A defocus series of colloidal gold particles allowed us to estimate the experimental contrast transfer function of the microscope. Images taken of several organic materials have shown high contrast for low atomic number elements and a resolution of 2.5 nm. The materials studied here include thin films of the organic semiconductor pentacene, triblock copolymer films, single-molecule dendrimers, electrospun polymer fibers and gold nanoparticles.     

Imaging colloidal gold labels in LVSEM

On biological samples, the topographic imaging capabilities of the new generation of scanning electron microscopes (SEM) (those having both field-emission guns and low aberration lenses) rival those of the replica techniques. In addition, they permit the localization of specific molecules on the sample surface using one of several labeling techniques utilizing heavy metal colloids. Normally, colloidal gold can be detected in the SEM both by the secondary electron signal (shape) and by the backscattered electron signal (BSE, Z-contrast). The new instruments seem to produce their best topographic images using low-beam voltage (1–5 kV) where topographic contrast is higher and the required thickness of the metal coating is less (Haggis and Pawley 1988, Ris and Pawley 1988). Although the detection of backscattered electrons is more difficult at low-beam voltage, we are able to show here that the secondary electron (SE) signal produced with a 2–5-kV beam permits the unambiguous detection of gold particles as small as 5 nm on carbon-coated specimens while a 1-kV beam produces a high-quality topographic image of the same sample.     

Preliminary Study of Nano- and Microscale TiO2 Additives on Tribological Behavior of Chemically Modified Rapeseed Oil

This study compared the tribological evaluation of chemically modified rapeseed oil as a potential biodegradable automotive lubricant with and without nano- and microscale titanium dioxide (TiO₂) particles, focusing on the influence of TiO₂ particles to improve the friction reduction and antiwear characteristics of chemically modified rapeseed oil. TiO₂ nano- and microscale particles of anatase phase and rutile phase were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Further, the analysis of chemically modified rapeseed oil with and without TiO₂ additives was carried out to determine its tribological behavior using a pin-on-disc tribometer. The experimental results showed that the addition of TiO₂ nanoparticles exhibited good friction reduction and antiwear properties compared with the addition of microscale TiO₂ and without TiO₂ additives to chemically modified rapeseed oil. Nanoscale TiO₂ is suitable as an antiwear additive in chemically modified rapeseed oil.     

A turbulent friction and heat transfer study of dispersed fluids with ultra-micronized metallic particles

Turbulent friction and heat transfer behaviors of dispersed fluids with ultra-micronized metallic particles are experimentally investigated in a circular pipe. Viscosity measurements are also conducted by using a viscometer. Aqueous mixtures with γ-Al₂O₃ and TiO₂ particles of which the mean diameters are 13 and 27 nm, respectively, are used to represent the dispersed fluids. The ranges of Reynolds and Prandtl numbers tested are 10⁴～10⁵ and 5.6～10.7, respectively. The relative viscosity of the dispersed fluid with γ-Al₂O₃ particles is about two hundred at the 10% volume concentration, while that of the dispersed fluid with TiO₂ particles is about twenty at the same volume concentration. Both of the relative viscosities are the unexpected results compared with predictions from classical theory of suspension rheology. Darcy friction factors for the comparatively dilute dispersion fluids used in present study coincide well with Kays correlation for tubulent flow of a single phase fluid, which implies that additional pumping power is not required despite adding solid particles into water. The Nusselt number of both the dispersed fluids for fully developed turbulent flow increases with increasing the volume concentration as well as the Reynolds number as expected. At the maximum volume concentration of 3% approximately, the percentage heat transfer enhancement due to addition of particles for the γ-Al₂O₃ and TiO₂ dispersing fluid systems are 60% and 30%, respectively. Under the range of volume concentration in the present study, the new correlation for turbulent convective heat transfer for both of the dispersed fluids is given by the following equation: Nu=0.021Re^0.8Pr.^0.5     

Interferometric investigation of the opto‐mechanical and structural properties of iPP/TiO2 nanocomposite fibers

Fibers that missing specific features and functionalities could be innovated and functionalised via nano additives, in particular metal oxides. Titanium oxide (TiO₂) nanoparticles have been added to isotactic polypropylene (iPP) to form iPP/TiO₂ nanocomposite fibers. Three samples of iPP/TiO₂ fibers were extruded at three extrusion speeds 25, 50, and 78 m/min were considered in this study. Mach–Zehnder interferometer was used to assess the changes in the opto‐mechanical and geometrical parameters of iPP/TiO₂ nanocomposite fibers along the fiber axis. The mechanical drawing device along with Mach–Zehnder interferometer was utilized to stretch the filaments to different draw ratios. The effect of mechanical cold drawing and extrusion speed on the optical and physical characteristics of iPP/TiO₂ nanocomposite fibers were determined along the fiber axis. The optical and physical variation along the nanocomposite samples were characterized by measuring their refractive indices, birefringence, refractive index profile along the fiber axis. The diffraction of He–Ne laser beam was used to define the variation of the fiber diameter along the fiber axis through their cross‐sectional area and shape. A sample of uniform diameter from neat iPP fibers was used as reference material for studying the variation of the iPP/TiO₂ fiber diameter along the fiber axis. As result, the iPP/TiO₂ nanocomposite fibers exhibited nonuniform diameters. The dispersion of TiO₂ particles in nanocomposite fibers influences the properties' consistency along and across the fiber.     

Scanning (atomic) force microscopy imaging of earthworm haemoglobin calibrated with spherical colloidal gold particles

Scanning (atomic) force microscopy (SFM) permits high-resolution imaging of a biological specimen in physiological solutions. Untreated extracellular haemoglobin molecules of the common North American earthworm, Lumbricus terrestris, were imaged in NH₄Ac solution using calibrated SFM. Individual molecules and their top and side views were clearly identified and were comparable with the images of the same molecule obtained by scanning transmission electron microscopy (STEM). A central depression, the presumed mouth of the hole, was detected. We analysed 75 individual molecules for their lateral dimensions. Compression varied for different molecules, presumably because of the variation of the interaction between the SFM tip and the protein molecule. Two effective heights which correspond to the heights of the points of the haemoglobin molecules first and last touched by the tip, h₁ and h₂, respectively, were measured for each protein and ranged between 1.58 and 16.2 nm for h₁ and 1.23 and 13.6 nm for h₂. The apparent diameter was measured and ranged from 44.9 to 86.6 nm (63.2±10.5 nm, n =75), which is about twice the diameter of the molecule reported by STEM for the top view orientation. The higher the measured effective heights, the worse was the tip convolution effect. In order to determine the tip parameters (semivertical angle, curvature of radius and the cut-off height) and to calibrate images of earthworm haemoglobin molecules, spherical gold particles were scanned as standards. The tip sectional radii at distances of h₁ and h₂ above the tip apex were subtracted from the apparent diameter of the protein. The calibrated lateral dimension was 29.1 ±3.85 nm, which is close to the reported scanning transmission electron microscopy data 30.0 ±0.8 nm. The results presented here demonstrate that the calibration approach of imaging gold particles is practical and relatively accurate. Calibrated SFM imaging can be applied to the study of other biomacromolecules.     

Measurement of magnetic domain wall width using energy-filtered Fresnel images

Magnetic domain walls in Nd₂Fe₁₄B have been examined using a series of energy‐filtered Fresnel images in the field emission gun transmission electron microscope (FEGTEM). We describe the changes in the intensity distribution of the convergent wall image as a function of defocus, foil thickness and domain wall width. The effect of tilted domain walls and beam convergence on the fringe pattern is also discussed. A comparison of the experimental intensity profile with that from simulations allows the domain wall width to be determined. Measurement of very narrow walls is made possible only by using a relatively thick foil, which necessitates energy‐filtering to allow quantitative comparison with simulations. The magnetic domain wall width in Nd₂Fe₁₄B was found to be 3 ± 2 nm.