Who made the noise? Systematic approach for the assessment of neutron imaging scintillators.

We propose a method to analyze the characteristics of scintillator screens for neutron imaging applications. Using calculations based on the theory of cascaded linear steps as well as experimental measurements, we compared the characteristics of different lithium- and gadolinium-based scintillator screens. Our results show that, despite their much lower light output, gadolinium-based scintillators outperform lithium-based scintillators in terms of noise characteristics for a variety of imaging setups. However, the relative performance of scintillator screens is highly dependent on the other setup characteristics such as the beam spectrum, field of view, used optical lens and size of the camera sensor. Consequently, the selection of the best scintillator screen - as well as the scintillator characteristics assessment in new developments - requires a systematic consideration of all these elements, as enabled by the framework presented here.

Operando Neutron Imaging.

In the past, neutron imaging has been the little brother of advanced neutron spectroscopy techniques due to its apparent simplicity. However, this simplicity allows the studying of complex chemical and electrochemical processes and related devices even under harsh reaction conditions such as high pressure, high temperature, corrosive and/or air sensitive environments. We review a number of highly relevant case studies as archetypal examples of modern energy technology; that is heat storage, power-to-X, batteries, fuel cells, and catalysis. The promising results trigger the further development of neutron imaging towards a chemical imaging method.

Dataset of the liquid water distribution in a biomimetic PEM fuel cell.

This dataset gathers the initial formation and the evolution of water content and distribution, as well as water evacuation, within a lung-inspired PEM (proton exchange membrane) fuel cell with a 50 cm2 active area for various operating conditions such as cell pressure, relative humidity of the reactant (anode and cathode), temperature, and cell current density. Neutron imaging was used since it has been shown to be an effective technique for quantitative analysis of water distribution, obtaining the thickness of the water with the Lambert-Beer law, thus obtaining the numerical data that composes the tables and graphs in this dataset. A series of videos compiling the individual images obtained through neutron imaging, showing the water distribution evolution are presented. Numerical and graphical compilation of the amount of water in a cell through time in different regions of the cell and for a total of 10 experiments are provided. This dataset provides a deeper knowledge on the complex phenomena that liquid water is subjected to in fuel cells along time, as well as a basis for an experimental validation for Computational Fluid Dynamics (CFD) simulations.

Revealing the impact of temperature in battery electrolytes via wavelength-resolved neutron imaging.

Understanding the limitations of electrolyte mixtures under extreme conditions is key to ensure reliable and safe battery performance. Among advanced characterization methods, time-of-flight neutron imaging (ToF-NI) is unique for its capability to map physicochemical changes of H-containing materials inside metallic casings and battery packs. The technique, however, requires long exposures in pulsed sources, which limits its applicability, particularly for analysis at low temperatures. To overcome these limitations, we use high-duty cycle ToF-NI at a continuous source, demonstrating its capability to expose physical and chemical changes of electrolytes due to variations in the overall molecular diffusion. The strategy described in this work reduces the exposure required and provides the baseline to study the thermal stability of electrolyte mixtures, from the proofing of state-of-the-art electrolyte mixtures up to their performance in batteries. This analysis and methodology apply to hydrogenous materials well beyond electrolytes for a wide range of applications.

Prospects of spectroscopic neutron imaging: optimizing experimental setups in battery electrolyte research.

Spectral neutron imaging methods provide valuable insights into the characterization of hydrogenous materials, including battery electrolytes. However, their application is constrained by sample geometry, setup parameters, and material chemistries, especially when studying physico-chemical changes in battery electrolytes. To address these limitations, we present a framework for simulating and optimizing the investigation of hydrogenous materials. Our approach combines quantitative modeling with experimental data to predict and optimize the contrast achievable in wavelength-resolved neutron imaging methods, thereby maximizing the information obtained in specific neutron imaging setups. While initially demonstrated at the BOA beamline of the Paul Scherrer Institute, this framework is applicable to any continuous source with spectral neutron imaging capabilities with a chopper disk. This work establishes a pathway for accurate studies of hydrogenous materials and their physico-chemical behavior, paving the way for advancements in the field of material characterization with wavelength-resolved neutron imaging.

Effects of Hydrophobicity Treatment of Gas Diffusion Layers on Ice Crystallization in Polymer Electrolyte Fuel Cells.

The unassisted cold-start capability of polymer electrolyte fuel cells (PEFCs) remains challenging for large-scale automotive applications. Various studies have shown that the freezing of produced water at the cathode catalyst layer (CL) and gas diffusion layer (GDL) interface blocks the oxidant gas and leads to a cold-start failure. However, the impact of GDL properties, including substrate, size, and hydrophobicity, on the freezing behavior of supercooled water is yet to be thoroughly investigated. We use differential scanning calorimetry to perform non-isothermal calorimetric measurements on untreated and waterproofed GDLs (Toray TGP-H-060, Freudenberg H23). By conducting a large number of experiments (>100) for each type of GDL, we obtained the corresponding distribution of onset freezing temperature (Tonset) and found noticeable sample-to-sample variations in both untreated and waterproofed GDLs. Furthermore, ice crystallization is affected by GDL wettability, coating load, coating distribution, and GDL size, whereas the impact of the GDL substrate and saturation level is not apparent. The Tonset distribution allows for predicting the capability of PEFC freeze-start and the freezing probability of residual water at a given subzero temperature. Our work paves the way for GDL modifications toward the improved cold-start capability of PEFC by identifying and avoiding the features that systematically trigger the freezing of supercooled water with high probability.

Absorption of pressurized methane in normal and supercooled p-xylene revealed via high-resolution neutron imaging.

Supercooling of liquids leads to peculiarities which are scarcely studied under high-pressure conditions. Here, we report the surface tension, solubility, diffusivity, and partial molar volume for normal and supercooled liquid solutions of methane with p-xylene. Liquid bodies of perdeuterated p-xylene (p-C8D10), and, for comparison, o-xylene (o-C8D10), were exposed to pressurized methane (CH4, up to 101 bar) at temperatures ranging 7.0-30.0 °C and observed at high spatial resolution (pixel size 20.3 µm) using a non-tactile neutron imaging method. Supercooling led to the increase of diffusivity and partial molar volume of methane. Solubility and surface tension were insensitive to supercooling, the latter substantially depended on methane pressure. Overall, neutron imaging enabled to reveal and quantify multiple phenomena occurring in supercooled liquid p-xylene solutions of methane under pressures relevant to the freeze-out in the production of liquefied natural gas.

Taurine Electrografting onto Porous Electrodes Improves Redox Flow Battery Performance.

The surface properties of porous carbonaceous electrodes govern the performance, durability, and ultimately the cost of redox flow batteries (RFBs). State-of-the-art carbon fiber-based electrode interfaces suffer from limited kinetic activity and incomplete wettability, fundamentally limiting the performance. Surface treatments for electrodes such as thermal and acid activation are a common practice to make them more suitable for aqueous RFBs; however, these treatments offer limited control over the desired functional properties. Here, we propose, for the first time, electrografting as a facile, rapid, and versatile technique to enable task-specific functionalization of porous carbonaceous electrodes for use in RFBs. Electrografting allows covalent attachment of organic molecules on conductive substrates upon application of an electrochemical driving force, and the vast library of available organic molecules can unlock a broad range of desired functional properties. To showcase the potential of electrografting for RFBs, we elect to investigate taurine, an amine with a highly hydrophilic sulfonic acid tail. Oxidative electrografting with cyclic voltammetry allows covalent attachment of taurine through the amine group to the fiber surface, resulting in taurine-functionalized carbon cloth electrodes. In situ polarization and impedance spectroscopy in single-electrolyte flow cells reveal that taurine-treated cloth electrodes result in 40% lower charge transfer and 25% lower mass transfer resistances than off-the-shelf cloth electrodes. We find that taurine-treated electrode interfaces promote faster Fe3+ reduction reaction kinetics as the electrochemical surface area normalized current densities are 2-fold and 4-fold higher than oxidized and untreated glassy carbon surfaces, respectively. Improved mass transfer of taurine-treated electrodes is attributed to their superior wettability, as revealed by operando neutron radiography within a flow cell setup. Through demonstrating promising results for aqueous systems with the model molecule taurine, this work aims to bring forth electrografting as a facile technique to tailor electrode surfaces for other RFB chemistries and electrochemical technologies.

Wicking dynamics in yarns.

The spontaneous imbibition of a liquid within porous media, known as wicking, can display uncommon features in textiles and yarns. Yarns exhibited step-wise wicking dynamics not captured by current models. HYPOTHESIS: Wicking dynamics in yarns not only depend on inter-fiber pore filling, but are mainly determined by the pore-to-pore transition processes and the structure of the pore network. EXPERIMENTS: Fast X-ray tomographic microscopy is employed to reveal the pore scale processes and neutron radiography for the macroscopic water uptake in yarns. A semi-empirical pore network model is presented that employs the measured pore network topology and pore scale dynamics to reproduce the experimentally observed wicking dynamics in yarns. FINDINGS: The yarn pore system is a sparse network of long and narrow pores that promotes step-wise uptake dynamics. Wicking in yarns displays fast pore filling events in the order of seconds and long waiting times between filling events up to several minutes while navigating the pore network. As main result, we find that a few filling events directly determine the macroscopic behavior of wicking in the sparse pore network of yarns. It is necessary to consider pore-to-pore transition waiting times and the pore network structure to explain the characteristics of wicking dynamics in yarns.

Neutron Imaging of Paramagnetic Ions: Electrosorption by Carbon Aerogels and Macroscopic Magnetic Forces.

The electrosorption of Gd3+ ions from an aqueous 70 mM Gd(NO3)3 solution in monolithic carbon aerogel electrodes was recorded by dynamic neutron imaging. The aerogels have a bimodal pore size distribution consisting of macropores and mesopores centered at 115 and 15 nm, respectively. After the uptake of Gd3+ ions by the negatively charged surface of the porous structure, an inhomogeneous magnetic field was applied to the system of discharging electrodes. This led to a convective flow and confinement of Gd(NO3)3 solution in the magnetic field gradient. Thus, a way to desalt and capture paramagnetic ions from an initially homogeneous solution is established.

Thermodynamics and Dynamics of Supercritical Water Pseudo-Boiling.

Supercritical fluid pseudo-boiling (PB), recently brought to the attention of the scientific community, is the phenomenon occurring when fluid changes its structure from liquid-like (LL) to gas-like (GL) states across the Widom line. This work provides the first quantitative analysis on the thermodynamics and the dynamics of water's PB, since the understanding of this phase transition is mandatory for the successful implementation of technologies using supercritical water (scH2O) for environmental, energy, and nanomaterial applications. The study combines computational techniques with in situ neutron imaging measurements. The results demonstrate that, during isobaric heating close to the critical point, while water density drops by a factor of three in the PB transitional region, the system needs >16 times less energy to increase its temperature by 1 K than to change its structure from LL to GL phase. Above the PB-Widom line, the structure of LL water consists mainly of tetramers and trimers, while below the line mostly dimers and monomers form in the GL phase. At atomic level, the PB dynamics are similar to those of the subcritical water vaporization. This fundamental knowledge has great impact on water science, as it helps to establish the structure-properties relationship of scH2O.

Frame overlap Bragg edge imaging.

Neutron Bragg edge imaging enables spatially resolved studies of crystalline features through the exploitation and analysis of Bragg edges in the transmission spectra recorded in each pixel of an imaging detector. Studies with high spectral resolutions, as is required e.g. for high-resolution strain mapping, and with large wavelength ranges have been largely reserved to pulsed neutron sources. This is due to the fact, that the efficiency for high wavelength resolution measurements is significantly higher at short pulse sources. At continuous sources a large fraction of the available neutrons must be sacrificed in order to achieve high wavelength resolution for a relevant bandwidth e.g. through a chopper system. Here we introduce a pulse overlap transmission imaging technique, which is suited to increase the available flux of high wavelength resolution time-of-flight neutron Bragg edge imaging at continuous neutron sources about an order of magnitude. Proof-of-principle measurements utilizing a chopper with a fourfold repeated random slit distribution of eight slits were performed at a thermal neutron beamline. It is demonstrated, that disentanglement of the overlapping pulses is achieved with the correlation theorem for signal processing. Thus, the Bragg edge pattern can be reconstructed from the strongly overlapping Bragg edge spectra recorded and the results demonstrate the feasibility of the technique.

One-pot neutron imaging of surface phenomena, swelling and diffusion during methane absorption in ethanol and n-decane under high pressure.

We report a powerful method for capturing the time-resolved concentration profiles, liquid swelling and surface phenomena during the absorption of methane (CH4) in still liquid ethanol (C2D6O) and n-decane (n-C10D22) and at high spatial resolution (pixel size 21.07 µm) using neutron imaging. Absorption of supercritical methane was followed at two temperatures and two pressures of methane, namely 7.0, 37.8 °C and 80, 120 bar. Fick's second law, which was used in the liquid-fixed coordinates, enabled for an adequate parameterization of the observed concentration profiles and liquid levels using simple analytical expressions. For both studied liquids, anomalously slow diffusion was observed in the initial stage of the absorption experiment. This was ascribed to the slow formation of the surface excess on the interface, time constant ranged 130-275 s. The axial symmetry of the cell allowed for the tomographic reconstructions of the profiles of the menisci. Based on these profiles, contact angle and surface tension were evaluated using the Young-Laplace equation. Overall, neutron imaging made it possible to capture time- and space-resolved information from which the methane concentration, liquid level and meniscus shape under high-pressure conditions inside a cylindrical titanium vessel were quantitatively derived. Multiple characteristics of ethanol, a methane hydrate inhibitor, and n-decane, a model constituent of crude oil, were thus measured for the first time under industrially relevant conditions in a one-pot experiment.

Laser-Engraved Textiles for Engineering Capillary Flow and Application in Microfluidics.

Steering capillary flow in textiles is of great significance in developing affordable and portable microfluidics devices. However, owing to the complex fibrous network, it remains a great challenge to achieve capillary flows with precise filling fronts. Here, an in situ laser engraving route is reported to accurately and rapidly etch textiles for manipulating capillary flow. The heterogeneity of the textile structure is enhanced because of the directional spreading of molten fibers polymer under the control of surface energy minimization. The principle of achieved anisotropic wicking of a water droplet in laser-engraved textiles is proposed. This understanding enables patterning the filling front of a fluid in different shapes, including arrow, straight line, diamond, and annulus. Precise capillary flow in textile-based microfluidics can benefit application in many fields, such as chemical analysis, biological detection, materials synthesis, multiliquid delivery. The laser engraving strategy has the advantages of simplicity, full scalability, and time rapidity, which provides an efficient avenue to steer capillary flow in diverse textiles for manufacturing customized microfluidic devices.

Coating Distribution Analysis on Gas Diffusion Layers for Polymer Electrolyte Fuel Cells by Neutron and X-ray High-Resolution Tomography.

Coating load and distribution in gas diffusion layers (GDLs) for polymer electrolyte fuel cells (PEFCs) have a major influence on mass transport losses. To be able to optimize the coating distribution and get more accurate data about the influence of the coating on the PEFC performance, better characterization techniques are necessary. Common analysis techniques are limited to selected sections of the material, or they are not sensitive to small amounts of coating. We propose a new methodology to get a complete description of the coating distribution and the GDL structure by combining high-resolution X-ray tomography with high-resolution neutron tomography. Using an isotopic gadolinium staining method to enhance the neutron and X-ray absorption contrast, lower quantities of coating can be detected. The combination of both imaging techniques allows for a more detailed analysis of the coating distribution.

Visualization of supercritical water pseudo-boiling at Widom line crossover.

Supercritical water is a green solvent used in many technological applications including materials synthesis, nuclear engineering, bioenergy, or waste treatment and it occurs in nature. Despite its relevance in natural systems and technical applications, the supercritical state of water is still not well understood. Recent theories predict that liquid-like (LL) and gas-like (GL) supercritical water are metastable phases, and that the so-called Widom line zone is marking the crossover between LL and GL behavior of water. With neutron imaging techniques, we succeed to monitor density fluctuations of supercritical water while the system evolves rapidly from LL to GL as the Widom line is crossed during isobaric heating. Our observations show that the Widom line of water can be identified experimentally and they are in agreement with the current theory of supercritical fluid pseudo-boiling. This fundamental understanding allows optimizing and developing new technologies using supercritical water as a solvent.

Visualization and quantification of inhomogeneous and anisotropic magnetic fields by polarized neutron grating interferometry.

The intrinsic magnetic moment of a neutron, combined with its charge neutrality, is a unique property which allows the investigation of magnetic phenomena in matter. Here we present how the utilization of a cold polarized neutron beam in neutron grating interferometry enables the visualization and characterization of magnetic properties on a microscopic scale in macroscopic samples. The measured signal originates from the phase shift induced by the magnetic potential. Our method enables the detection of previously inaccessible magnetic field gradients, in the order of T cm-1, extending the probed range by an order of magnitude. We visualize and quantify the phase shift induced by a well-defined square shaped uniaxial magnetic field and validate our experimental findings with theoretical calculations based on Hall probe measurements of the magnetic field distribution. This allows us to further extend our studies to investigations of inhomogeneous and anisotropic magnetic field distribution.

Implementation and assessment of the black body bias correction in quantitative neutron imaging.

We describe in this paper the experimental procedure, the data treatment and the quantification of the black body correction: an experimental approach to compensate for scattering and systematic biases in quantitative neutron imaging based on experimental data. The correction algorithm is based on two steps; estimation of the scattering component and correction using an enhanced normalization formula. The method incorporates correction terms into the image normalization procedure, which usually only includes open beam and dark current images (open beam correction). Our aim is to show its efficiency and reproducibility: we detail the data treatment procedures and quantitatively investigate the effect of the correction. Its implementation is included within the open source CT reconstruction software MuhRec. The performance of the proposed algorithm is demonstrated using simulated and experimental CT datasets acquired at the ICON and NEUTRA beamlines at the Paul Scherrer Institut.

In situ diagnostics of the crystal-growth process through neutron imaging: application to scintillators.

Neutrons are known to be unique probes in situations where other types of radiation fail to penetrate samples and their surrounding structures. In this paper it is demonstrated how thermal and cold neutron radiography can provide time-resolved imaging of materials while they are being processed (e.g. while growing single crystals). The processing equipment, in this case furnaces, and the scintillator materials are opaque to conventional X-ray interrogation techniques. The distribution of the europium activator within a BaBrCl:Eu scintillator (0.1 and 0.5% nominal doping concentrations per mole) is studied in situ during the melting and solidification processes with a temporal resolution of 5-7 s. The strong tendency of the Eu dopant to segregate during the solidification process is observed in repeated cycles, with Eu forming clusters on multiple length scales (only for clusters larger than ∼50 µm, as limited by the resolution of the present experiments). It is also demonstrated that the dopant concentration can be quantified even for very low concentration levels (∼0.1%) in 10 mm thick samples. The interface between the solid and liquid phases can also be imaged, provided there is a sufficient change in concentration of one of the elements with a sufficient neutron attenuation cross section. Tomographic imaging of the BaBrCl:0.1%Eu sample reveals a strong correlation between crystal fractures and Eu-deficient clusters. The results of these experiments demonstrate the unique capabilities of neutron imaging for in situ diagnostics and the optimization of crystal-growth procedures.

Engineered Water Highways in Fuel Cells: Radiation Grafting of Gas Diffusion Layers.

A novel method to produce gas diffusion layers with patterned wettability for fuel cells is presented. The local irradiation and subsequent grafting permits full design flexibility and wettability tuning, while modifying throughout the whole material thickness. These water highways have improved operando performance due to an optimized water management inside the cells.