The understanding of solid–gas interactions has been greatly advanced over the past decade on account of the availability of high-resolution transmission electron microscopes (TEMs) equipped with differentially pumped environmental cells. The operational pressures in these differentially pumped environmental TEM (DP-ETEM) instruments are generally limited up to 20 mbar. Yet, many industrial catalytic reactions are operated at pressures equal or higher than 1 bar—50 times higher than that in the DP-ETEM. This poses limitations for in situ study of gas reactions through ETEM and advances are needed to extend in situ TEM study of gas reactions to the higher pressure range. Here, we present a first series of experiments using a gas flow membrane cell TEM holder that allows a pressure up to 4 bar. The built-in membrane heaters enable reactions at a temperature of 95–400°C with flowing reactive gases. We demonstrate that, using a conventional thermionic TEM, 2 Å atomic fringes can be resolved with the presence of 1 bar O2 gases in an environmental cell and we show real-time observation of the Kirkendall effect during oxidation of cobalt nanocatalysts.

Since it was discovered in 2004, graphene has attracted enormous attention as an emerging material for future devices, but it has been found that conventional lithographic processes based on polymer resist degrade its intrinsic performance. Recently, our group studied a resist-free scanning tunneling microscopy-based lithography in various atmospheres by injecting volatile liquids into a chamber. In this study, multilayer graphene was scanned and etched by controlling bias voltage under methanol pressure. We focused on improving patterning results in terms of depth and line width, while the previous study was performed to find an optimum gas environment for patterning on a graphite surface. Specifically, we report patterning outputs depending on conditions of voltage, current, and pressure. The optimum conditions for methanol environment etching were a gas pressure in the range of 41–50 torr, a −4 V tip bias, and a 2 nA tunneling current.

Transmission electron microscopy characterization of two major long-period stacking ordered (LPSO) phases in Mg–Zn–Y alloy, i.e., 18R- and 14H-LPSO are reported. The space group and atomic-scale microstructures of both compounds were determined using a combination of electron diffraction, convergent beam electron diffraction, high-resolution transmission electron microscopy, and Z-contrast scanning transmission electron microscopy. The 18R-LPSO phase is demonstrated to have a point group and space group 3m and R3m (or 3m and R3m), with the lattice parameter a = 1.112 nm and c = 4.689 nm in a hexagonal coordinate system. The 14H-LPSO phase has a point group 6/mmm and a space group P63 /mmc, and the lattice parameter is a = 1.112 nm and c = 3.647 nm. In addition, insertion of extra thin Mg platelets of several atomic layers, results in stacking faults in the LPSO phase. These results may shed some new light on a better understanding of the microstructure and deformation mechanisms of LPSO phases in Mg alloys.

A multi-scale investigation of twin bundles in Fe–22Mn–0.6C (wt%) twinning-induced plasticity steel after tensile deformation has been carried out by truly correlative means; using electron channelling contrast imaging combined with electron backscatter diffraction, high-resolution secondary ion mass spectrometry, scanning transmission electron microscopy, and atom probe tomography on the exact same region of interest in the sample. It was revealed that there was no significant segregation of Mn or C to the twin boundary interfaces.

Electron energy-loss spectroscopy (EELS) attached to current transmission electron microscopes can probe not only element-selective chemical information, but also site-selective information that depends on the position that a specific element occupies in a crystal lattice. The latter information is exploited by utilizing the Bloch waves symmetry in the crystal, which changes with its orientation with respect to the incident electron wave (electron channeling). We demonstrate the orientation dependence of the cross-section of the electron energy-loss near-edge structure for particular crystalline sites of spinel ferrites, by quantitatively taking into account the dynamical diffraction effects with a large number of the diffracted beams. The theoretical results are consistent with a set of experiments in which the transition metal sites in spinel crystal structures are selectively excited. A new measurement scheme for site-selective EELS using a two-dimensional position-sensitive detector is proposed and validated by theoretical predictions and trial experiments.

A fast method for determination of the Co-valence state by electron energy loss spectroscopy in a transmission electron microscope is presented. We suggest the distance between the Co-L3 and Co-L2 white-lines as a reliable property for the determination of Co-valence states between 2+ and 3+. The determination of the Co-L2,3 white-line distance can be automated and is therefore well suited for the evaluation of large data sets that are collected for line scans and mappings. Data with a low signal-to-noise due to short acquisition times can be processed by applying principal component analysis. The new technique was applied to study the Co-valence state of Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF), which is hampered by the superposition of the Ba-M4,5 white-lines on the Co-L2,3 white-lines. The Co-valence state of the cubic BSCF phase was determined to be 2.2+ (±0.2) after annealing for 100 h at 650°C, compared to an increased valence state of 2.8+ (±0.2) for the hexagonal phase. These results support models that correlate the instability of the cubic BSCF phase with an increased Co-valence state at temperatures below 840°C.

Solid particles in snow deposits, sampled in mining and Pb-processing area of Žerjav, Slovenia, have been investigated using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS). Identified particles were classified as geogenic–anthropogenic, anthropogenic, and secondary weathering products. Geogenic–anthropogenic particles were represented by scarce Zn- and Pb-bearing ore minerals, originating from mine waste deposit. The most important anthropogenic metal-bearing particles in snow were Pb-, Sb- and Sn-bearing oxides and sulphides. The morphology of these particles showed that they formed at temperatures above their melting points. They were most abundant in snow sampled closest to the Pb-processing plant and least abundant in snow taken farthest from the plant, thus indicating that Pb processing was their predominant source between the last snowfall and the time of sampling. SEM/EDS analysis showed that Sb and Sn contents in these anthropogenic phases were higher and more variable than in natural Pb-bearing ore minerals. The most important secondary weathering products were Pb- and Zn-containing Fe-oxy-hydroxides whose elemental composition and morphology indicated that they mostly resulted from oxidation of metal-bearing sulphides emitted from the Pb-processing plant. This study demonstrated the importance of single particle analysis using SEM/EDS for differentiation between various sources of metals in the environment.

Vickers microindentation and Berkovich nanoindentation tests were carried out on a polycrystalline nickel (Ni) bulk specimen. Electron channeling contrast imaging (ECCI) in conjunction with electron backscattered diffraction was used to image and characterize plastic deformation inside and around the indents using a field emission scanning electron microscope. The ECCI was performed with a 5 keV beam energy and 0° tilt specimen position. The strain field distribution, slip lines, and Taylor lattices were imaged on an indented surface. Orientation mapping was used to investigate the local crystallographic misorientation and identify specific ⟨110⟩ slip systems. An ion milling surface preparation technique was used to remove materials from the surface which permitted the study of deformed microstructure below the indent. A dislocation density of 1011 cm−2 was calculated based on the curvature of bend contours observed in the ECCI micrographs obtained from the Vickers indents. A yield strength of 500 MPa was calculated based on the size of the strain field measured from the ECCI micrographs of the nanoindents. The combination of ion milling, ECCI, and electron backscattered diffraction was shown to be beneficial to investigate the indentation-induced plastic deformation in a polycrystalline Ni bulk specimen.

This work establishes a multiscale and multitechnique nondestructive approach as valid methodology for monitoring surface properties and evaluating the effectiveness of enzymatic removal of varnishes from paintings/polychrome artefacts.

Mock-up samples (documented reconstructions of oil, tempera, and gilded layers on canvas and wooden supports) were covered with different proteinaceous varnishes (egg white, animal and fish glue, casein) and then characterized before and after the removal of these coatings with enzyme-based solutions. The varnish was cleaned in several steps (two dry swabs and two wet swabs) with a clearance step for removing the residues from proteinaceous varnish or from enzyme solution.

Microscopy [stereomicroscopy (SM), optical microscopy (OM), atomic force microscopy (AFM), and scanning electron microscopy (SEM)] and colorimetric (CIE L*a*b* system) techniques were used for characterization of the reconstruction surfaces at different scales (macro-scale by SM and OM; micro-scale by SEM and nano-scale by AFM). These techniques were also used to monitor the cleaning treatment.

Although results presented in this work were obtained for the specific treatment of enzyme removal, the methodology could be extended to other types of materials and cleaning. Further experiments on real works of art are needed for a complete validation of the methodology.

In Romanesque wall paintings in Aragon (Spain), the pigment used for creating blue was a very characteristic mineral, aerinite, which came from local ores in the southern Pyrenees. Optical and scanning electron microscopy (SEM), with energy-dispersive X-ray (EDX) analysis, X-ray diffraction, and reflectance spectroscopy were used to make a detailed microcharacterization of this rare blue pigment in order to improve the knowledge of its composition and possible variability, from samples of medieval paintings and some mineral ores. New analytical data on the chemical composition of the blue pigment are reported here, together with the characterization of its microstructure, and the heterogeneity of the natural pigment made by the features of the ore itself. X-ray diffraction pattern and color parameters of the mineral ores are also included. The data obtained by SEM-EDX will assist identification of this pigment by electron microscopy. The natural variability in composition observed in the samples may be used to explain formation of the extracted mineral and to compare several ore sources. Connection of the ore composition with the pigments used in Romanesque wall paintings will help both provenance and attribution studies.

As part of an ongoing effort to increase image reproducibility and fidelity in addition to improving cross-instrument consistency, we have proposed using four separate instrument quality tests to augment the ones we have previously reported. These four tests assessed the following areas: (1) objective lens quality, (2) resolution, (3) accuracy of the wavelength information from spectral detectors, and (4) the accuracy and quality of spectral separation algorithms. Data were received from 55 laboratories located in 18 countries. The largest source of errors across all tests was user error which could be subdivided between failure to follow provided protocols and improper use of the microscope. This truly emphasizes the importance of proper rigorous training and diligence in performing confocal microscopy experiments and equipment evaluations. It should be noted that there was no discernible difference in quality between confocal microscope manufactures. These tests, as well as others previously reported, will help assess the quality of confocal microscopy equipment and will provide a means to track equipment performance over time. From 62 to 97% of the data sets sent in passed the various tests demonstrating the usefulness and appropriateness of these tests as part of a larger performance testing regiment.

Electron tomography is becoming one of the most used methods for structural analysis at nanometric scale in biological and materials sciences. Combined with chemical mapping, it provides qualitative and semiquantitative information on the distribution of chemical elements on a given sample. Due to the current difficulties in obtaining three-dimensional (3D) maps by energy-filtered transmission electron microscopy (EFTEM), the use of 3D chemical mapping has not been widely adopted by the electron microscopy community. The lack of specialized software further complicates the issue, especially in the case of data with a low signal-to-noise ratio (SNR). Moreover, data interpretation is rendered difficult by the absence of efficient segmentation tools. Thus, specialized software for the computation of 3D maps by EFTEM needs to include optimized methods for image series alignment, algorithms to improve SNR, different background subtraction models, and methods to facilitate map segmentation. Here we present a software package (EFTEM-TomoJ, which can be downloaded from http://u759.curie.fr/fr/download/softwares/EFTEM-TomoJ), specifically dedicated to computation of EFTEM 3D chemical maps including noise filtering by image reconstitution based on multivariate statistical analysis. We also present an algorithm named BgART (for background removing algebraic reconstruction technique) allowing the discrimination between background and signal and improving the reconstructed volume in an iterative way.

Though three-dimensional (3D) imaging gives deep insight into the inner structure of complex materials, the stereological analysis of 2D snapshots of material sections is still necessary for large-scale industrial applications for reasons related to time and cost constraints. In this paper, we propose an original framework to estimate the orientation distribution of generalized cylindrical structures from a single 2D section. Contrary to existing approaches, knowledge of the cylinder cross-section shape is not necessary. The only requirement is to know the area distribution of the cross-sections. The approach relies on minimization of a least squares criterion under linear equality and inequality constraints that can be solved with standard optimization solvers. It is evaluated on synthetic data, including simulated images, and is applied to experimental microscopy images of fibrous composite structures. The results show the relevance and capabilities of the approach though some limitations have been identified regarding sensitivity to deviations from the assumed model.

A forescatter electron detector (FSED) was used to acquire dark-field micrographs (DF-FSED) on thin specimens with a scanning electron microscope. The collection angles were adjusted with the detector distance from the beam axis, which is similar to the camera length of the scanning transmission electron microscope annular DF detectors. The DF-FSED imaging resolution was calculated with SMART-J on an aluminum alloy and carbon nanotubes (CNTs) decorated with platinum nanoparticles. The resolution was three to six times worse than with bright-field imaging. Measurements of nanometer-size objects showed a similar feature size in DF-FSED imaging despite a signal-to-noise ratio 12 times smaller. Monte Carlo simulations were used to predict the variation of the contrast of a CNT/Fe/Pt system as a function of the collection angles. It was constant for very high collection angles (>450 mrad) and confirmed experimentally. The reverse contrast between carbon black particles and the smallest titanium dioxide (TiO2) nanoparticles was predicted by Monte Carlo simulations and observed in the DF-FSED micrograph of a battery electrode coating. However, segmentation of the micrograph was not able to isolate the TiO2 nanoparticle phase because of the close contrast of small TiO2 nanoparticles compared to the C black particles.

Conventional electron-probe microanalysis has an X-ray analytical spatial resolution on the order of 1–4 μm width/depth. Many of the naturally occurring Fe–Si compounds analyzed in this study are smaller than 1 μm in size, requiring the use of lower accelerating potentials and nonstandard X-ray lines for analysis. Problems with the use of low-energy X-ray lines (soft X-rays) of iron for quantitative analyses are discussed and a review is given of the alternative X-ray lines that may be used for iron at or below 5 keV (i.e., accelerating voltage that allows analysis of areas of interest <1 μm). Problems include increased sensitivity to surface effects for soft X-rays, peak shifts (induced by chemical bonding, differential self-absorption, and/or buildup of carbon contamination), uncertainties in the mass attenuation coefficient for X-ray lines near absorption edges, and issues with spectral resolution and count rates from the available Bragg diffractors. In addition to the results from the traditionally used Fe Lα line, alternative approaches, utilizing Fe Lβ, and Fe Ll-η lines, are discussed.

Atom probe is a nanoscale technique for creating three-dimensional spatially and chemically resolved point datasets, primarily of metallic or semiconductor materials. While atom probe can achieve local high-level resolution, the spatial coherence of the technique is highly dependent upon the evaporative physics in the material and can often result in large geometric distortions in experimental results. The distortions originate from uncertainties in the projection function between the field evaporating specimen and the ion detector. Here we explore the possibility of continuum numerical approximations to the evaporative behavior during an atom probe experiment, and the subsequent propagation of ions to the detector, with particular emphasis placed on the solution of axisymmetric systems, such as isolated particles and multilayer systems. Ultimately, this method may prove critical in rapid modeling of tip shape evolution in atom probe tomography, which itself is a key factor in the rapid generation of spatially accurate reconstructions in atom probe datasets.