Philippe Gasser

Three-dimensional analysis of porous BaTiO3 ceramics using FIB nanotomography

Three‐dimensional (3D) data represent the basis for reliable quantification of complex microstructures. Therefore, the development of high‐resolution tomography techniques is of major importance for many materials science disciplines. In this paper, we present a novel serial sectioning procedure for 3D analysis using a dual‐beam FIB (focused ion beam). A very narrow and reproducible spacing between the individual imaging planes is achieved by using drift correction algorithms in the automated slicing procedure. The spacing between the planes is nearly of the same magnitude as the pixel resolution on scanning electron microscopy images. Consequently, the acquired stack of images can be transformed directly into a 3D data volume with a voxel resolution of 6 × 7 × 17 nm. To demonstrate the capabilities of FIB nanotomography, a BaTiO3 ceramic with a high volume fraction of fine porosity was investigated using the method as a basis for computational microstructure analysis and the results compared with conventional physical measurements. Significant differences between the particle size distributions as measured by nanotomography and laser granulometry indicate that the latter analysis is skewed by particle agglomeration/aggregation in the raw powder and by uncertainties related to calculation assumptions. Significant differences are also observed between the results from mercury intrusion porosimetry (MIP) and 3D pore space analysis. There is strong evidence that the ink‐bottle effect leads to an overestimation of the frequency of small pores in MIP. FIB nanotomography thus reveals quantitative information of structural features smaller than 100 nm in size which cannot be acquired easily by other methods.

Bow-tie optical antenna probes for single-emitter scanning near-field optical microscopy

A method for the fabrication of bow-tie optical antennas at the apex of pyramidal Si3N4 atomic force microscopy tips is described. We demonstrate that these novel optical probes are capable of sub-wavelength imaging of single quantum dots at room temperature. The enhanced and confined optical near-field at the antenna feed gap leads to locally enhanced photoluminescence (PL) of single quantum dots. Photoluminescence quenching due to the proximity of metal is found to be insignificant. The method holds promise for single quantum emitter imaging and spectroscopy at spatial resolution limited by the engineered antenna gap width exclusively.

The influence of constrictivity on the effective transport properties of porous layers in electrolysis and fuel cells

The aim of the present investigation is to define microstructure parameters, which control the effective transport properties in porous materials for energy technology. Recent improvements in 3D-imaging (FIB-nanotomography, synchrotron X-ray tomography) and image analysis (skeletonization and graph analysis, transport simulations) open new possibilities for the study of microstructure effects. In this study, we describe novel procedures for a quantitative analysis of constrictivity, which characterizes the so-called bottleneck effect. In a first experimental part, methodological tests are performed using a porous (La,Sr)CoO3 material (SOFC cathode). The tests indicate that the proposed procedure for quantitative analysis of constrictivity gives reproducible results even for samples with inhomogeneous microstructures (cracks, gradient of porosity). In the second part, 3D analyses are combined with measurements of ionic conductivity by impedance spectroscopy. The investigations are preformed on membranes of electrolysis cells with porosities between 0.27 and 0.8. Surprisingly, the tortuosities remain nearly constant (1.6) for the entire range of porosity. In contrast, the constrictivities vary strongly and correlate well with the measured transport resistances. Hence, constrictivity represents the dominant microstructure parameter, which controls the effective transport properties in the analysed membrane materials. An empirical relationship is then derived for the calculation of effective transport properties based on phase volume fraction, tortuosity, and constrictivity.

TEM-specimen preparation of cell/mineral interfaces by Focused Ion Beam milling

Abstract Picocyanobacteria were found to play an important role in calcite precipitation in oligotrophic lakes. In this study, investigations on the interface between cyanobacteria and attached biogenic calcite crystals have been performed to gain further insights into the mechanisms of nucleation of these precipitates. Ultramicrotomy, the conventional preparation technique of thin sections for Transmission Electron Microscopy (TEM) investigations, often fails when working on heterogeneous samples containing soft organic material and hard minerals. Thus, in this study the thin sections were prepared using Focused Ion Beam (FIB) milling. This approach is usually applied in material sciences but until recently was not very common in environmental research. Different analytical TEM methods like Electron Spectroscopic Imaging (ESI) and Electron Energy Loss Spectrometry (EELS) were used to test the suitability of FIB-milling for the preparation of organic/inorganic interface specimens. With this approach we were able to analyze both organic and the inorganic phases of the same sample. Elemental maps of the samples were also calculated. By analyzing the structure of the C K-absorption edge, the different bonding forms of the organic carbon cell and the inorganic carbon of the crystal could be clearly distinguished

Study of microstructure and interfaces in an aluminium–C60 composite material

Abstract This work deals with the study of microstructure and interfacial reactions in an aluminium–fullerene (Al/C 60 ) composite produced by pressurized liquid metal infiltration (squeeze casting) of a tap-packed C 60 powder preform. The obtained composite shows a homogeneous distribution of C 60 crystals in the Al matrix, indicating that the original aggregated crystalline structure of the C 60 fullerenes was not disrupted during the composite fabrication process, even though there is evidence of partial sublimation of C 60 . The C 60 crystals are well integrated in the matrix and there is no hint either of porosity or of weak interfacial bonding. At the interface between Al and C 60 rod-shaped and hexagonal plate-like phases are occasionally observed by TEM. These phases were identified as Al 4 C 3 by XRD and Raman spectroscopy and were shown to nucleate on very thin layers of amorphous carbon at the surface of the C 60 crystals.

Bridging microscopes: 3D correlative light and scanning electron microscopy of complex biological structures.

The rationale of correlative light and electron microscopy (CLEM) is to collect data on different information levels--ideally from an identical area on the same sample--with the aim of combining datasets at different levels of resolution to achieve a more holistic view of the hierarchical structural organization of cells and tissues. Modern three-dimensional (3D) imaging techniques in light and electron microscopy opened up new possibilities to expand morphological studies into the third dimension at the nanometer scale and over various volume dimensions. Here, we present two alternative approaches to correlate 3D light microscopy (LM) data with scanning electron microscopy (SEM) volume data. An adapted sample preparation method based on high-pressure freezing for structure preservation, followed by freeze-substitution for multimodal en-bloc imaging or serial-section imaging is described. The advantages and potential applications are exemplarily shown on various biological samples, such as cells, individual organisms, human tissue, as well as plant tissue. The two CLEM approaches presented here are per se not mutually exclusive, but have their distinct advantages. Confocal laser scanning microscopy (CLSM) and focused ion beam-SEM (FIB-SEM) is most suitable for targeted 3D correlation of small volumes, whereas serial-section LM and SEM imaging has its strength in large-area or -volume screening and correlation. The second method can be combined with immunocytochemical methods. Both methods, however, have the potential to extract statistically relevant data of structural details for systems biology.

Site-specific specimen preparation by focused ion beam milling for transmission electron microscopy of metal matrix composites.

This work describes the application and usefulness of the focused ion beam (FIB) technique for the preparation of transmission electron microscopy (TEM) samples from metal matrix composite materials. Results on an Aldiamond composite, manufactured by the squeeze casting infiltration process, were chosen for demonstration. It is almost impossible to prepare TEM specimens of this material by any other conventional method owing to the presence of highly inhomogeneous phases and reinforcement diamond particles. The present article gives a detailed account of the salient features of the FIB technique and its operation. One of the big advantages is the possibility to prepare site-specific TEM specimens with high spatial resolution. The artifacts occurring during the specimen preparation, for example, Ga-ion implantation, curtain effects, amorphous layers, bending of the lamella, or different milling behaviors of the materials have been discussed. Furthermore, TEM examination of the specimens prepared revealed an ultrafine amorphous layer of graphite formed at the interface between the Al and diamond particles that may affect the interfacial properties of the composite materials. This may not have been feasible without the successful application of the FIB technique for production of good quality site-specific TEM specimens.

Cryo-FIB-nanotomography for quantitative analysis of particle structures in cement suspensions.

Cryo‐FIB‐nanotomography is a novel high‐resolution 3D‐microscopy technique, which opens new possibilities for the quantitative microstructural analysis of complex suspensions. In this paper, we describe the microstructural changes associated with dissolution and precipitation processes occurring in a fresh cement paste, which has high alumina and sulphate contents. During the first 6 min, precipitation of ettringite leads to a general decrease of the particle size distribution. In the unhydrated cement paste almost no particles smaller than 500 nm are present, whereas after 6 min this size class already represents 9 vol%. The precipitation of ettringite also leads to a significant increase of the particle number density from 0.294*109/mm3 at t0min to 20.55*109/mm3 at t6min. Correspondingly the surface area increases from 0.75 m2/g at t0min to 2.13 m2/g at t6min. The small ettringite particles tend to form agglomerates, which strongly influence the rheological properties. The particular strength of cryo‐FIB‐nt is the potential to quantify particle structures in suspension and thereby also to describe higher‐order topological features such as the particle–particle interfaces, which is important for the study of agglomeration processes.

Focussed ion beam nanotomography reveals the 3D morphology of different solid phases in hardened cement pastes

Due to the development of integrated low‐keV back‐scattered electron detectors, it has become possible in focussed ion beam nanotomography to segment not only solid matter and porosity of hardened cement paste, but also to distinguish different phases within the solid matter. This paper illustrates a method that combines two different approaches for improving the contrast between different phases in the solid matrix of a cement paste. The first approach is based on the application of a specially developed 3D diffusion filter. The second approach is based on a modified data‐acquisition procedure during focussed ion beam nanotomography. A pair of electron images is acquired for each slice in the focussed ion beam nanotomography dataset. The first image is captured immediately after ion beam milling; the second image is taken after a prolonged exposure to electron beam scanning. The acquisition of complementary focussed ion beam nanotomography datasets and processing the images with a 3D anisotropic diffusion filter allows distinguishing different phases within the hydration products.

3D Microstructure Effects in Ni-YSZ Anodes: Prediction of Effective Transport Properties and Optimization of Redox Stability

This study investigates the influence of microstructure on the effective ionic and electrical conductivities of Ni-YSZ (yttria-stabilized zirconia) anodes. Fine, medium, and coarse microstructures are exposed to redox cycling at 950 °C. FIB (focused ion beam)-tomography and image analysis are used to quantify the effective (connected) volume fraction (Φeff), constriction factor (β), and tortuosity (τ). The effective conductivity (σeff) is described as the product of intrinsic conductivity (σ0) and the so-called microstructure-factor (M): σeff = σ0 × M. Two different methods are used to evaluate the M-factor: (1) by prediction using a recently established relationship, Mpred = εβ0.36/τ5.17, and (2) by numerical simulation that provides conductivity, from which the simulated M-factor can be deduced (Msim). Both methods give complementary and consistent information about the effective transport properties and the redox degradation mechanism. The initial microstructure has a strong influence on effective conductivities and their degradation. Finer anodes have higher initial conductivities but undergo more intensive Ni coarsening. Coarser anodes have a more stable Ni phase but exhibit lower YSZ stability due to lower sintering activity. Consequently, in order to improve redox stability, it is proposed to use mixtures of fine and coarse powders in different proportions for functional anode and current collector layers.