Beat Münch

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.

Stripe and ring artifact removal with combined wavelet — Fourier filtering

A fast, powerful and stable filter based on combined wavelet and Fourier analysis for the elimination of horizontal or vertical stripes in images is presented and compared with other types of destriping filters. Strict separation between artifacts and original features allowing both, suppression of the unwanted structures and high degree of preservation of the original image information is endeavoured. The results are validated by visual assessments, as well as by quantitative estimation of the image energy loss. The capabilities and the performance of the filter are tested on a number of case studies related to applications in tomographic imaging. The case studies include (i) suppression of waterfall artifacts in electron microscopy images based on focussed ion beam nanotomography, (ii) removal of different types of ring artifacts in synchrotron based X-ray microtomography and (iii) suppression of horizontal stripe artifacts from phase projections in grating interferometry.

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.

Fast reconstruction algorithm dealing with tomography artifacts

Highly brilliant X-rays delivered by third generation synchrotron facilities coupled with modern detector technology permit routinely acquisition of high resolution tomograms in few minutes, making high throughput experiments a reality and bringing real-time tomography closer. New solutions for fast post-processing of such large amount of data are mandatory to fully exploit advantages provided by the high acquisition speed enabling new experiments until recently even unimaginable. The TOMCAT beamline1 is well equipped for fast and high throughput experiments2, 3. Here, we will focus on our solutions regarding the reconstruction process and discuss a fast reconstruction algorithm4, based on the Fourier Transform method as opposed to slower standard Filtered Back-Projection routines. We perform the critical step of such method, the polar-to-Cartesian mapping in the Fourier space, by convolution with the Fourier transform of functions with particular characteristics. This convolution approach combines speed with accuracy, making real-time data postprocessing closer to reality. This fast reconstruction algorithm implemented at TOMCAT also features several plug-ins, aimed at taming reconstruction artifacts. Here, we will discuss a new approach for removing rings from reconstructed datasets arising from defective detector pixels and/or damaged scintillator screens. This new method is based on a combined wavelet- FFT decomposition5. Another important feature of the presented reconstruction algorithm deals with local tomographic datasets, characterized by incomplete data. We show here that ad-hoc padding of the sinograms prior to reconstruction significantly reduces typical artifacts related to data incompleteness, making local tomography a valuable acquisition mode when small volumes in relatively large samples are of interest.

Spatiotemporal computed tomography of dynamic processes

Modern computed tomography (CT) equipment allowing fast 3-D imaging also makes it possible to monitor dynamic processes by 4-D imaging. Because the acquisition time of various 3-D-CT systems is still in the range of at least milliseconds or even hours, depending on the detector system and the source, the balance of the desired temporal and spatial resolution must be adjusted. Furthermore, motion artifacts will occur, especially at high spatial resolution and longer measuring times. We propose two approaches based on nonsequential projection angle sequences allowing a convenient postacquisition balance of temporal and spatial resolution. Both strategies are compatible with existing instruments, needing only a simple reprograming of the angle list used for projection acquisition and care with the projection order list. Both approaches will reduce the impact of artifacts due to motion. The strategies are applied and validated with cold neutron imaging of water desorption from originally saturated particles during natural air-drying experiments and with x-ray tomography of a polymer blend heated during imaging.

Quantification of fly ash in hydrated, blended Portland cement pastes by backscattered electron imaging

An automated image analysis procedure for the segmentation of anhydrous fly ash from backscattered electron images of hydrated, fly ash blended Portland cement paste is presented. A total of six hundred backscattered electron images per sample are acquired at a magnification of 2000. Characteristic features of fly ash particles concerning grey level, shape and texture were used to segment anhydrous fly ash by a combination of grey level filtering, grey level segmentation and morphological filtering techniques. The thresholds for the grey level segmentation are determined for each sample by semiautomatic histogram analysis of the full image stack of each sample. The analysis of the presented dataset reveals a standard deviation of the reaction degree of fly ash of up to 4.3%. The results agree with a selective dissolution method to quantify the reaction degree of fly ash showing the potential of the presented image analysis procedure.

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.

Toward Reproducible Three-Dimensional Microstructure Analysis of Granular Materials and Complex Suspensions

Focused ion beam nanotomography (FIB-nt) is a novel method for high resolution three-dimensional (3D) imaging. In this investigation we assess the methodological parameters related to image acquisition and data processing that are critical for obtaining reproducible microstructural results from granular materials and from complex suspensions. For this purpose three case studies are performed: (1) The precision of FIB-nt is evaluated by analyzing a reference sample with nanospheres. Due to the implementation of an automated correction procedure, drift phenomena can be removed largely from the FIB data. However, at high magnifications remaining drift components can induce problems for 3D-shape reconstructions. (2) Correct object recognition from densely packed microstructures requires specific algorithms for splitting of agglomerated particles. To establish quantitative criteria for the correct degree of splitting, a parametric study with dry portland cement is performed. It is shown that splitting with a k-value of 0.6 leads to accurate results. (3) Finally, the reproducibility of the entire cryo-FIB analysis is investigated for high pressure frozen cement suspensions. Reproducible analyses can be obtained if the magnification is adapted to the particle size. At low magnifications the small particles and their surface area are underestimated. At high magnifications representativity is questioned because local inhomogeneities can become dominant.

3D microstructure effects in Ni-YSZ anodes : influence of TPB lengths on the electrochemical performance

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance (Rpol). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance. However, the quantitative results also show that there is no simplistic relationship between TPB and Rpol. The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and Rpol. In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPBactive by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPBactive, effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer.

Quantification of a Single Aggregate Inner Porosity and Pore Accessibility Using Hard X-ray Phase-Contrast Nanotomography

The 3D structure of three individual aggregates composed of 165 nm polystyrene primary particles is revealed nondestructively by hard X-ray phase-contrast synchrotron nanotomography. Three-dimensional image analysis allows us for the first time to obtain the complex inner porosity of the entire aggregate. It is demonstrated that despite their rather compact structure, characterized by a fractal dimension equal to 2.7, the produced aggregates are still porous, with porosity increasing with its size. Generated pores have diameters from 100 nm to 3 μm and are almost completely interconnected.