Time-resolved in situ tomography for the analysis of evolving metal-foam granulates.

An experimental setup has been developed that allows for capturing up to 25 tomograms s-1 using the white X-ray beam at the experimental station EDDI of BESSY II, Berlin, Germany. The key points are the use of a newly developed, precise and fast rotation stage, a very efficient scintillator and a fast CMOS camera. As a first application, the foaming of aluminium alloy granules at 923 K was investigated in situ. Formation and growth of bubbles in the liquid material were observed and found to be influenced by the limited thermal conductivity in the bulk granules. Changes that took place between two tomographic frames separated in time by 39 ms could be detected and analysed quantitatively.

Simultaneous X-ray radioscopy/tomography and energy-dispersive diffraction applied to liquid aluminium alloy foams.

High-speed X-ray imaging in two dimensions (radioscopy) and three dimensions (tomography) is combined with fast X-ray diffraction in a new experimental setup at the synchrotron radiation source BESSY II. It allows for in situ studies of time-dependent phenomena in complex systems. As a first application, the foaming process of an aluminium alloy was studied in three different experiments. Radioscopy, optical expansion measurements and diffraction were used to correlate the change of foam morphology to the various phases formed during heating of an AlMg15Cu10 alloy to 620°C in the first experiment. Radioscopy was then replaced by tomography. Acquiring tomograms and diffraction data at 2 Hz allows even more details of foam evolution to be captured, for example, bubble size distribution. In a third experiment, 4 Hz tomography yields dynamic insights into fast phenomena in evolving metal foam.

Slow crystallisation of a monodisperse foam stabilised against coarsening.

The evolution of a three-dimensional monodisperse foam was investigated using X-ray tomography over the course of seven days. The coarsening of the sample was inhibited through the use of perfluorohexane gas. The internal configuration of bubbles is seen to change markedly, evolving from a disordered arrangement towards a more ordered state. We chart this ordering process through the use of the coordination number, the bond orientational order parameter (BOOP) and the translational order parameter.

Hierarchical radioscopy using polychromatic and partially coherent hard synchrotron radiation.

Pushing synchrotron x-ray radiography to increasingly higher image-acquisition rates (currently up to 100,000 fps) while maintaining spatial resolutions in the micrometer range implies drastically reduced fields of view. As a consequence, either imaging a small subregion of the sample with high spatial resolution or only the complete specimen with moderate resolution is applicable. We introduce a concept to overcome this limitation by making use of a semi-transparent x-ray detector positioned close to the investigated sample. The hard x-rays that pass through the sample either create an image on the first detector or keep on propagating until they are captured by a second x-ray detector located further downstream. In this way, a process can be imaged simultaneously in a hierarchical manner within a single exposure and a projection of the complete object with moderate resolution as well as a subregion with high resolution are obtained. As a proof-of-concept experiment, image sequences of an evolving liquid-metal foam are shown, employing frame rates of 1000 images/s (1.2 µm pixel size) and 15,000 images/s (18.1 µm pixel size) for the first and second detector, respectively.

Tem-per-ature dependence in Bragg edge neutron transmission measurements.

A systematic study has been carried out to investigate the neutron transmission signal as a function of sample tem-per-ature. In particular, the experimentally de-ter-mined wavelength-dependent neutron attenuation spectra for a martensitic steel at tem-per-atures ranging from 21 to 700°C are com-pared with simulated data. A theoretical description that includes the Debye-Waller factor in order to describe the tem-per-ature influence on the neutron cross sections was im-plemented in the nxsPlotter software and used for the simulations. The analysis of the attenuation coefficients at varying tem-per-atures shows that the missing contributions due to elastic and inelastic scattering can be clearly distinguished: while the elastically scattered intensities decrease with higher tem-per-atures, the inelastically scattered intensities increase, and the two can be separated from each other by analysing unique sharp features in the form of Bragg edges. This study presents the first systematic approach to qu-antify this effect and can serve as a basis , for example, to correct measurements taken during in situ heat treatments, in many cases being a prerequisite for obtaining qu-anti-fiable results.

Quantitative structural assessment of heterogeneous catalysts by electron tomography.

We present transmission electron microscope (TEM) tomography investigations of ruthenium-based fuel cell catalyst materials as employed in direct methanol fuel cells (DMFC). The digital three-dimensional representation of the samples not only enables detailed studies on number, size, and shape but also on the local orientation of the ruthenium particles to their support and their freely accessible surface area. The shape analysis shows the ruthenium particles deviate significantly from spherical symmetry which increases their surface to volume ratio. The morphological studies help to understand the structure formation mechanisms during the fabrication as well as the high effectiveness of these catalysts in the oxygen reduction reaction at the cathode side of fuel cells.

The Neutron Imaging Instrument CONRAD-Post-Operational Review.

The neutron imaging instrument CONRAD was operated as a part of the user program of the research reactor BER-II at Helmholtz-Zentrum Berlin (HZB) from 2005 to 2020. The instrument was designed to use the neutron flux from the cold source of the reactor, transported by a curved neutron guide. The pure cold neutron spectrum provided a great advantage in the use of different neutron optical components such as focusing lenses and guides, solid-state polarizers, monochromators and phase gratings. The flexible setup of the instrument allowed for implementation of new methods including wavelength-selective, dark-field, phase-contrast and imaging with polarized neutrons. In summary, these developments helped to attract a large number of scientists and industrial customers, who were introduced to neutron imaging and subsequently contributed to the expansion of the neutron imaging community.

Tomoscopy: Time-Resolved Tomography for Dynamic Processes in Materials.

The structure and constitution of opaque materials can be studied with X-ray imaging methods such as 3D tomography. To observe the dynamic evolution of their structure and the distribution of constituents, for example, during processing, heating, mechanical loading, etc., 3D imaging has to be fast enough. In this paper, the recent developments of time-resolved X-ray tomography that have led to what one now calls "tomoscopy" are briefly reviewed A novel setup is presented and applied that pushes temporal resolution down to just 1 ms, that is, 1000 tomograms per second (tps) are acquired, while maintaining spatial resolutions of micrometers and running experiments for minutes without interruption. Applications recorded at different acquisition rates ranging from 50 to 1000 tps are presented. The authors observe and quantify the immiscible hypermonotectic reaction of AlBi10 (in wt%) alloy and dendrite evolution in AlGe10 (in wt%) casting alloy during fast solidification. The combustion process and the evolution of the constituents are analyzed in a burning sparkler. Finally, the authors follow the structure and density of two metal foams over a long period of time and derive details of bubble formation and bubble ageing including quantitative analyses of bubble parameters with millisecond temporal resolution.

Hardness data related to pre-ageing, natural secondary ageing, and paint bake hardening in Al-Mg-Si alloys.

The effect of pre-ageing (PA) time and temperature on subsequent natural secondary ageing (NSA) and paint bake (PB) hardening of an AA6014 Al-Mg-Si alloy was systematically investigated, especially when both parameters change. A wide range of PA conditions was covered with temperatures ranging from 80 °C to 160 °C and times from several minutes to several days depending on the PA temperature. Hardness data for such pre-treatments measured by Brinell method are given. Hardness data measured during NSA are fitted by various functions. This dataset might be reused for further kinetic analysis of the clustering in Al-Mg-Si alloys or for the determination of the optimal PA tactics for industrial production.

In†situ and Operando Tracking of Microstructure and Volume Evolution of Silicon Electrodes by using Synchrotron X-ray Imaging.

The internal microstructure of a silicon electrode in a lithium ion battery was visualized by operando synchrotron X-ray radioscopy during battery cycling. The silicon particles were found to change their sizes upon lithiation and delithiation and the changes could be quantified. It was found that volume change of a particle is related to its initial size and is also largely determined by the changing surrounding electron-conductive network and internal interface chemical environment (e.g., electrolyte migration, solid-electrolyte interphase propagation) within fractured particles. Moreover, an expansion prolongation phenomenon was discovered whereby some particles continue expanding even after switching the battery current direction and shrinkage would be expected, which is explained by assuming different expansion characteristics of particle cores and outer regions. The study provides new basic insights into processes inside Si particles during lithiation and delithiation and also demonstrates the unique possibilities of operando synchrotron X-ray imaging for studying degradation mechanisms in battery materials.

Using X-ray tomoscopy to explore the dynamics of foaming metal.

The complex flow of liquid metal in evolving metallic foams is still poorly understood due to difficulties in studying hot and opaque systems. We apply X-ray tomoscopy -the continuous acquisition of tomographic (3D) images- to clarify key dynamic phenomena in liquid aluminium foam such as nucleation and growth, bubble rearrangements, liquid retraction, coalescence and the rupture of films. Each phenomenon takes place on a typical timescale which we cover by obtaining 208 full tomograms per second over a period of up to one minute. An additional data processing algorithm provides information on the 1 ms scale. Here we show that bubble coalescence is not only caused by gravity-induced drainage, as experiments under weightlessness show, and by stresses caused by foam growth, but also by local pressure peaks caused by the blowing agent. Moreover, details of foam expansion and phenomena such as rupture cascades and film thinning before rupture are quantified. These findings allow us to propose a way to obtain foams with smaller and more equally sized bubbles.

An X-ray Tomographic Study of Rechargeable Zn/MnO2 Batteries.

We present non-destructive and non-invasive in operando X-ray tomographic investigations of the charge and discharge behavior of rechargeable alkaline-manganese (RAM) batteries (Zn-MnO2 batteries). Changes in the three-dimensional structure of the zinc anode and the MnO2 cathode material after several charge/discharge cycles were analyzed. Battery discharge leads to a decrease in the zinc particle sizes, revealing a layer-by-layer dissolving behavior. During charging, the particles grow again to almost their initial size and shape. After several cycles, the particles sizes slowly decrease until most of the particles become smaller than the spatial resolution of the tomography. Furthermore, the number of cracks in the MnO2 bulk continuously increases and the separator changes its shape. The results are compared to the behavior of a conventional primary cell that was also charged and discharged several times.

In Operando Quantification of Three-Dimensional Water Distribution in Nanoporous Carbon-Based Layers in Polymer Electrolyte Membrane Fuel Cells.

Understanding the function of nanoporous materials employed in polymer electrolyte membrane fuel cells (PEMFCs) is crucial to improve their performance, durability, and cost efficiency. Up to now, the water distribution in the nm-sized pore structures was hardly accessible during operation of the cells. Here we demonstrate that phase contrast synchrotron X-ray tomography allows for an in operando quantification of the three-dimensional water distribution within the nm-sized pores of carbon-based microporous layers (MPLs). For this purpose, a fuel cell design optimized for tomographic phase contrast measurements was realized. Water in the pores of the entire MPL was detected and quantified. We found an inhomogeneous distribution of the local water saturation and a sharp boundary between mostly filled MPL and almost empty areas. We attribute the latter observation to the two-phase boundary created because condensation takes place predominantly on one side of the boundary. Furthermore, high water saturation in large areas hints at gas diffusion or transport along preferred three-dimensional paths through the material, therefore bypassing most of the MPL volume. Our approach may contribute significantly to future investigations of nanoporous fuel cell materials under realistic operating conditions.

Three-Dimensional Visualization of Gas Evolution and Channel Formation inside a Lithium-Ion Battery.

Gas generation within lithium ion batteries (LIBs) gives rise to safety concerns that question their applicability. By employing synchrotron X-ray imaging, the gas and channel evolution occurring in an operating LIB have been directly visualized in their inherent 3D state as a function of discharge and charge. Using the spatial 3D distribution of gas bubbles and channels, the active particles that dictate the performance of a functional LIB were identified and visualized in 3D. Delithiation and lithiation are interpreted as the process of activating particles continuously in a step-by-step way. The present work not only demonstrates the generation and evolution of gas within LIB in 3D, but also reveals the distribution of active particles for the first time. These fundamentally findings presented here shed light on a range of processes that could not previously be characterized in 3D and can provide practical guidance for the design of next-generation LIBs with improved safety.

In†Situ Radiographic Investigation of (De)Lithiation Mechanisms in a Tin-Electrode Lithium-Ion Battery.

The lithiation and delithiation mechanisms of multiple-Sn particles in a customized flat radiography cell were investigated by in situ synchrotron radiography. For the first time, four (de)lithiation phenomena in a Sn-electrode battery system are highlighted: 1) the (de)lithiation behavior varies between different Sn particles, 2) the time required to lithiate individual Sn particles is markedly different from the time needed to discharge the complete battery, 3) electrochemical deactivation of originally electrochemically active particles is reported, and 4) a change of electrochemical behavior of individual particles during cycling is found and explained by dynamic changes of (de)lithiation pathways amongst particles within the electrode. These unexpected findings fundamentaly expand the understanding of the underlying (de)lithiation mechanisms inside commercial lithium-ion batteries (LIBs) and would open new design principles for high-performance next-generation LIBs.

Morphological Evolution of Electrochemically Plated/Stripped Lithium Microstructures Investigated by Synchrotron X-ray Phase Contrast Tomography.

Due to its low redox potential and high theoretical specific capacity, Li metal has drawn worldwide research attention because of its potential use in next-generation battery technologies such as Li-S and Li-O2. Unfortunately, uncontrollable growth of Li microstructures (LmSs, e.g., dendrites, fibers) during electrochemical Li stripping/plating has prevented their practical commercialization. Despite various strategies proposed to mitigate LmS nucleation and/or block its growth, a fundamental understanding of the underlying evolution mechanisms remains elusive. Herein, synchrotron in-line phase contrast X-ray tomography was employed to investigate the morphological evolution of electrochemically deposited/dissolved LmSs nondestructively. We present a 3D characterization of electrochemically stripped Li electrodes with regard to electrochemically plated LmSs. We clarify fundamentally the origin of the porous lithium interface growing into Li electrodes. Moreover, cleavage of the separator caused by growing LmS was experimentally observed and visualized in 3D. Our systematic investigation provides fundamental insights into LmS evolution and enables us to understand the evolution mechanisms in Li electrodes more profoundly.

3D mapping of crystallographic phase distribution using energy-selective neutron tomography.

Nondestructive 3D mapping of crystallographic phases is introduced providing distribution of phase fractions within the bulk (centimeter range) of samples with micrometer-scale resolution. The novel neutron tomography based technique overcomes critical limitations of existing techniques and offers a wide range of potential applications. It is demonstrated for steel samples exhibiting phase transformation after being subjected to tensile and torsional deformation.

Mapping the evolution of hierarchical microstructures in a Ni-based superalloy.

Phase separation of γ' precipitates determines the microstructure and mechanical properties of nickel-based superalloys. In the course of ageing, disordered γ spheres form inside ordered (L12) γ' precipitates, undergo a morphological change to plates and finally split the γ' precipitates. The presence of γ particles inside γ' affects coarsening kinetics and increases alloy hardness. Here we use atom probe tomography to visualize phase separation in a Ni86.1Al8.5Ti5.4 alloy in three dimensions and to quantify the composition of all the phases with near-atomic resolution. We find that γ' precipitates are supersaturated in nickel, thereby driving the formation of γ particles and observe a compositional evolution of the γ particles, which accompanies their morphological change. Our results suggest that by controlling nickel supersaturation we can tailor the phase separation and thereby the properties of nickel-based superalloys.

Automated quantitative 3D analysis of faceting of particles in tomographic datasets.

Characterization of facets of particles is a common problem. In this paper an algorithm is presented which allows automated quantitative 3D analysis of facets of many particles within tomographic datasets. The algorithm is based on the analysis of probability distributions of the orientations of triangle normals of mesh representations. The result consists of lists containing number of detected facets, their size, global orientation and the interplanar angles between facets for each analyzed particle. Characterization of each particle according to any of these facet properties is then possible, e.g. statistics about different crystal shapes or removal of particles that do not show significant faceting. Analyses of a 3D dataset obtained by focused ion beam (FIB) tomography of a sample containing spinel particles are presented.