Bio-Inspired Ceramic?Metal Composites Using Ceramic 3D Printing and Centrifugal Infiltration
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Volumetric additive manufacturing (VAM) forms complete 3D objects in a single photocuring operation without layering defects, enabling 3D printed polymer parts with mechanical properties similar to their bulk material counterparts. This study presents the first report of VAM-printed thiol-ene resins. With well-ordered molecular networks, thiol-ene chemistry accesses polymer materials with a wide range of mechanical properties, moving VAM beyond the limitations of commonly used acrylate formulations. Since free-radical thiol-ene polymerization is not inhibited by oxygen, the nonlinear threshold response required in VAM is introduced by incorporating 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a radical scavenger. Tuning of the reaction kinetics is accomplished by balancing inhibitor and initiator content. Coupling this with quantitative measurements of the absorbed volumetric optical dose allows control of polymer conversion and gelation during printing. Importantly, this work thereby establishes the first comprehensive framework for spatial–temporal control over volumetric energy distribution, demonstrating structures 3D printed in thiol-ene resin by means of tomographic volumetric VAM. Mechanical characterization of this thiol-ene system, with varied ratios of isocyanurate and triethylene glycol monomers, reveals highly tunable mechanical response far more versatile than identical acrylate-based resins. This broadens the range of materials and properties available for VAM, taking another step toward high-performance printed polymers.
Porous carbonaceous electrodes are performance-defining components in redox flow batteries (RFBs), where their properties impact the efficiency, cost, and durability of the system. The overarching challenge is to simultaneously fulfill multiple seemingly contradictory requirements—i.e., high surface area, low pressure drop, and facile mass transport—without sacrificing scalability or manufacturability. Here, non-solvent induced phase separation (NIPS) is proposed as a versatile method to synthesize tunable porous structures suitable for use as RFB electrodes. The variation of the relative concentration of scaffold-forming polyacrylonitrile to pore-forming poly(vinylpyrrolidone) is demonstrated to result in electrodes with distinct microstructure and porosity. Tomographic microscopy, porosimetry, and spectroscopy are used to characterize the 3D structure and surface chemistry. Flow cell studies with two common redox species (i.e., all-vanadium and Fe2+/3+) reveal that the novel electrodes can outperform traditional carbon fiber electrodes. It is posited that the bimodal porous structure, with interconnected large (>50 µm) macrovoids in the through-plane direction and smaller (<5 µm) pores throughout, provides a favorable balance between offsetting traits. Although nascent, the NIPS synthesis approach has the potential to serve as a technology platform for the development of porous electrodes specifically designed to enable electrochemical flow technologies.
In the last decade, transmission X-ray microscopes (TXMs) have come into operation in most of the synchrotrons worldwide. They have proven to be outstanding tools for non-invasive ex and in situ 3D characterization of materials at the nanoscale across varying range of scientific applications. However, their spatial resolution has not improved in many years, while newly developed functional materials and microdevices with enhanced performances exhibit nanostructures always finer. Here, optomechanical breakthroughs leading to fast 3D tomographic acquisitions (85 min) with sub-10 nm spatial resolution, narrowing the gap between X-ray and electron microscopy, are reported. These new achievements are first validated with 3D characterizations of nanolithography objects corresponding to ultrahigh-aspect-ratio hard X-ray zone plates. Then, this powerful technique is used to investigate the morphology and conformality of nanometer-thick film electrodes synthesized by atomic layer deposition and magnetron sputtering deposition methods on 3D silicon scaffolds for electrochemical energy storage applications.
Abstract Ferroelectric domain walls are quasi‐2D systems that show great promise for the development of nonvolatile memory, memristor technology, and electronic components with ultrasmall feature size. Electric fields, for example, can change the domain wall orientation relative to the spontaneous polarization and switch between resistive and conductive states, controlling the electrical current. Being embedded in a 3D material, however, the domain walls are not perfectly flat and can form networks, which leads to complex physical structures. In this work, the importance of the nanoscale structure for the emergent transport properties is demonstrated, studying electronic conduction in the 3D network of neutral and charged domain walls in ErMnO 3 . By combining tomographic microscopy techniques and finite element modeling, the contribution of domain walls within the bulk is clarified and the significance of curvature effects for the local conduction is shown down to the nanoscale. The findings provide insights into the propagation of electrical currents in domain wall networks, reveal additional degrees of freedom for their control, and provide quantitative guidelines for the design of domain‐wall‐based technology.
Porous transport layers (PTL) and their surface properties have the potential to improve the performance of proton exchange membrane water electrolyzers (PEMWE), which is imperative to reduce feedstock costs and lead to their widespread implementation. This work introduces a novel generation of titanium microporous layers (MPLs) with ultra-low thicknesses of approx. 20 um which reduces raw material costs. They also feature advanced interfacial properties tailored to maximize catalyst utilization at low Ir-loadings. The bulk morphology and surface properties of the hierarchically structured PTLs are assessed by X-ray tomographic microscopy. The low surface roughness of the MPL allows the use of thinner membranes since it minimizes possible deformations in the membrane. Cells containing the MPLs outperformed those containing state-of-the-art commercially available PTL materials by up to 100 mV at 7 A cm-2 in combination with low-loaded catalyst-coated membranes of 0.4 mgIr cm-2. Hydrogen crossover is also reduced, especially at low current densities, leading to a larger turndown ratio which can enable more cost-effective operating strategies. Finally, these rationally designed MPLs also lead to high catalyst utilization by overcoming the naturally occurring high in-plane resistance of low-loaded catalyst layers.
With the increased production of electric vehicles to reduce carbon emissions, the lithium-ion battery market to supply those vehicles has grown dramatically. To enhance battery sustainability and circularity, direct recycling methods aim to recover intact cathode materials. However, end-of-life cathode materials are typically 15–20 years old and often have lower energy density compared to current cathode materials. To address this challenge, a rapid precipitation process is developed to boost energy density by converting low Ni-compositions, LiNi 0.33 Co 0.33 Mn 0.33 O 2 (NMC111), into higher Ni-compositions (NMC622). This process forms a Ni-rich coating on cathode particles that diffuses into the core upon high-temperature relithiation, increasing compositional homogeneity. The upcycling process leverages existing infrastructure, offering low capital cost and minimal additional chemical input. Through ex situ tomographic transmission X-ray microscopy (TXM), 3D Ni:Co elemental mixing is quantified, confirming that elemental content evens at the secondary particle level with a mean NMC622 composition upon relithiation. However, elemental gradients remain in the single crystalline primary particles. Ex situ high-resolution and in situ wide-angle X-ray diffraction reveals concurrent structural changes during the relithiation process. These findings provide key insights into the structural and chemical mechanisms of elemental diffusion to obtain further improvements of increased capacity and retention through compositional conversion of cathode materials.
The use of grazing-incidence scattering methods for the characterization of 2D patterned organic thin films is limited due to the elongated 1D footprint of the X-ray beam on the sample. However, this characteristic feature can be turned into an advantage, when combined with tomographic reconstruction. In this pilot study we show, how the use of a chosen texture reflection and a diffuse reflectivity signal can each provide 2D images of the deposits, simultaneously revealing the organic film's crystal orientation and the location of the metal electrodes in a field-effect transistor structure from a single sequence of diffraction images.
Purpose Digital breast tomosynthesis (DBT) is a limited‐angle tomographic breast imaging modality that can be used for breast cancer screening in conjunction with full‐field digital mammography (FFDM) or synthetic mammography (SM). Currently, there are five commercial DBT systems that have been approved by the U.S. FDA for breast cancer screening, all varying greatly in design and imaging protocol. Because the systems are different in technical specifications, there is a need for a quantitative approach for assessing them. In this study, the DBT systems are assessed using a novel methodology with an inkjet‐printed anthropomorphic phantom and four alternative forced choice (4AFC) study scheme. Method A breast phantom was fabricated using inkjet printing and parchment paper. The phantom contained 5‐mm spiculated masses fabricated with potassium iodide (KI)‐doped ink and microcalcifications (MCs) made with calcium hydroxyapatite. Images of the phantom were acquired on all five systems with DBT, FFDM, and SM modalities where available using beam settings under automatic exposure control. A 4AFC study was conducted to assess reader performance with each signal under each modality. Statistical analysis was performed on the data to determine proportion correct (PC), standard deviations, and levels of significance. Results For masses, overall detection was highest with DBT. The difference in PC was statistically significant between DBT and SM for most systems. A relationship was observed between increasing PC and greater gantry span. For MCs, performance was highest with DBT and FFDM compared to SM. The difference between PC of DBT and PC of SM was statistically significant for all manufacturers. Conclusions This methodology represents a novel approach for evaluating systems. This study is the first of its kind to use an inkjet‐printed anthropomorphic phantom with realistic signals to assess performance of clinical DBT imaging systems.
Detonation of a solid explosive produces a turbulent and luminous post‐detonation fireball containing condensed carbon soot. Diagnostics of soot dynamics are needed for model validation and to interpret emission signals. Diffuse back‐illumination extinction imaging (DBI‐EI) and laser‐induced incandescence (LII) are two common optical diagnostics for flame soot. This work extends both to measure time‐resolved soot dynamics from a 12 mm HMX hemisphere. DBI‐EI measured line‐of‐sight optical extinction exceeds 99% in some regions. Results are tomographically inverted to obtain a signal proportional to the soot volume fraction. Pulse‐burst LII measures are presented at 1 MHz. For the first time, LII results are combined with DBI‐EI extinction measurements to quantify and correct for signal trapping. Following this, spatially and temporally resolved DBI‐EI and LII measures are shown to be in reasonable agreement. Finally, experimental results are compared against recently developed simulations. Quantitative differences in the soot mixing dynamics are resolved. These findings motivate future model improvements and demonstrate ongoing needs for diagnostic advancements for heavily sooting environments.
Abstract In this study, we present a method of pattern mining based on network theory that enables the identification of protein structures or complexes from synthetic volume densities, without the knowledge of predefined templates or human biases for refinement. We hypothesized that the topological connectivity of protein structures is invariant, and they are distinctive for the purpose of protein identification from distorted data presented in volume densities. Three‐dimensional densities of a protein or a complex from simulated tomographic volumes were transformed into mathematical graphs as observables. We systematically introduced data distortion or defects such as missing fullness of data, the tumbling effect, and the missing wedge effect into the simulated volumes, and varied the distance cutoffs in pixels to capture the varying connectivity between the density cluster centroids in the presence of defects. A similarity score between the graphs from the simulated volumes and the graphs transformed from the physical protein structures in point data was calculated by comparing their network theory order parameters including node degrees, betweenness centrality, and graph densities. By capturing the essential topological features defining the heterogeneous morphologies of a network, we were able to accurately identify proteins and homo‐multimeric complexes from 10 topologically distinctive samples without realistic noise added. Our approach empowers future developments of tomogram processing by providing pattern mining with interpretability, to enable the classification of single‐domain protein native topologies as well as distinct single‐domain proteins from multimeric complexes within noisy volumes.
Direct reduced iron (DRI) is an increasingly important feedstock for modern steelmaking. Fundamental research into DRI properties is limited by the discrepancy between the behavior of industrially produced pellets and laboratory‐produced pellets, leading to nongeneralizable conclusions from laboratory work. Here, in this study, a detailed nano‐computed tomographic characterization of ore pellets, hydrogen DRI reduced in a pilot‐scale shaft furnace, and laboratory‐reduced DRI is presented to better understand the microstructurally influenced property differences between the two. The shaft‐furnace‐reduced pellets show lower overall porosity but larger average pore volume thickness and solid volume thickness than the laboratory‐reduced pellets. This effect is attributed to increased sintering behavior in the shaft furnace case. All pellet types show almost entirely connected pore volumes. The tortuosity of the pores is shown to increase with a degree of reduction, though the shaft furnace pellets show lower tortuosity than the laboratory‐reduced pellets. Again, this difference is attributed to the larger pore volume thickness for shaft‐furnace‐reduced pellets.
Abstract A function of global monitoring of nuclear explosions is the development of Earth models for predicting seismic travel times for more accurate calculation of event locations. Most monitoring agencies rely on fast, distance-dependent one-dimensional (1D) Earth models to calculate seismic event locations quickly and in near real-time. RSTT (Regional Seismic Travel Time) is a seismic velocity model and computer software package that captures the major effects of three-dimensional crust and upper mantle structure on regional seismic travel times, while still allowing for fast prediction speed (milliseconds). We describe updates to the RSTT model using a refined data set of regional phases (i.e., Pn, Pg, Sn, Lg) using the Bayesloc relative relocation algorithm. The tomographic inversion shown here acts to refine the previous RSTT public model ( rstt201404um ) and displays significant features related to areas of global tectonic complexity as well as further reduction in arrival residual values. Validation of the updated RSTT model demonstrates significant reduction in median epicenter mislocation (15.3 km) using all regional phases compared to the iasp91 1D model (22.1 km) as well as to the current station correction approach used at the Comprehensive Nuclear-Test-Ban Treaty Organization International Data Centre (18.9 km).
Abstract This work presents a novel numerical procedure for reconstructing volumetric density and velocity fields from planar laser-induced fluorescence (PLIF) and stereoscopic particle image velocimetry (SPIV) data. This new method is theoretically and practically demonstrated to provide more accurate 3D vortical structures and density fields in high shear flows than reconstruction methods based on the mean convective velocity. While Taylor’s hypothesis of frozen turbulence is commonly applied by using the local mean streamwise velocity, the proposed algorithm uses the measured local instantaneous velocity for data convection. It consists of a step-by-step reconstruction based on a mixed Lagrangian–Eulerian solver that includes the 3D interpolation of scattered flow data and that relaxes the Taylor’s hypothesis by iterative enforcement of the incompressibility constraint on the velocity field. This methodology provides 3D fields with temporal resolution, spatial resolution, and accuracy comparable to that of real 3D snapshots, thus providing a practical alternative to tomographic measurements. The procedure is validated using numerical data of the constant-density channel flow available on the Johns Hopkins University Turbulence Database (JHTDB), showing the accurate reconstruction of the 3D velocity field. The algorithm is applied to an experimental dataset of PLIF and SPIV measurements of a variable-density jet flow, demonstrating its capability to provide 3D velocity and density fields that are more consistent with the Navier–Stokes equations compared to the mean flow convective method. Graphic abstract
Extensive experimental research on high-pressure spray has been conducted for decades to deepen our understanding and optimize its use in transportation, aviation, and propulsion applications; however, the near-field and in-nozzle flow characteristics are not fully understood. Dense near-field spray is among the most challenging diagnostic tasks since light is severely scattered and diffused by the liquid droplets and columns. In this work, the near-field spray and in-nozzle flow characteristics of an aeration nozzle at elevated pressures were characterized by neutron radiography imaging at the Oak Ridge National Laboratory High Flux Isotope Reactor. Neutron imaging benefits via strong penetration depths for some metals (i.e., aluminum, lead, and steel) and is sufficiently sensitive to detection of light elements, especially for hydrogen-based molecules, due to the large incoherent scattering cross section of neutrons. Both two-dimensional snapshots of the near-field spray and a three-dimensional tomographic scan of the nozzle geometry and in-nozzle water were obtained. This work provides new quantitative characterization of practical metal nozzle geometry for accurate boundary conditions, internal flow patterns inside the nozzle, and high-pressure spray flows. In conclusion, the findings may be used to improve performance and operating conditions of transportation vehicles and propulsion systems.
Understanding mechanical failure, crack propagation, and compressive behavior at the micrometer scale is essential for tailoring material properties for structural performance in cellular materials. Typically, modeling of traditional polymer foam materials is clouded by the lack of control in material morphology and its inherent stochastic structure. Additive manufacturing with sub-micrometer resolution provides a direct path for experimenters to specifically tailor structures needed by modelers to explicitly probe mechanical performance. Using laboratory-based 3D X-ray computed tomographic imaging (CT), the examination of deformation and damage provides a critical path to understand how these soft materials behave. Additionally, synchrotron CT yields realistic information at higher strain rates to directly validate the robustness of our finite element modeling. For this study, nanolithographic printing was employed to generate a series of engineered lattices with increasing levels of defects through the random removal of ligaments. These structures were mechanically tested and imaged with laboratory-based microCT. Additionally, synchrotron experiments were conducted in which the structures were imaged in 3D at 14 Hz during compression at a 0.4 s –1 strain rate. These 3D images show the changes in the structure as the ligaments bend, buckle and fracture in real time. This technique provides a robust framework for developing our methodologies and future exploration of engineered structures.
Working within a vineyard in the Pessac Léognan Appellation of Bordeaux, France, this study documents the potential of using simple statistical methods with spatially-resolved and increasingly available electromagnetic induction (EMI) geophysical and normalized difference vegetation index (NDVI) datasets to accurately estimate Bordeaux vineyard soil classes and to quantitatively explore the relationship between vineyard soil types and grapevine vigor. First, co-located electrical tomographic tomography (ERT) and EMI datasets were compared to gain confidence about how the EMI method averaged soil properties over the grapevine rooting depth. Then, EMI data were used with core soil texture and soil-pit based interpretations of Bordeaux soil types (Brunisol, Redoxisol, Colluviosol and Calcosol) to estimate the spatial distribution of geophysically-identified Bordeaux soil classes. A strong relationship (r = 0.75, p < 0.01) was revealed between the geophysically-identified Bordeaux soil classes and NDVI (both 2 m resolution), showing that the highest grapevine vigor was associated with the Bordeaux soil classes having the largest clay fraction. The results suggest that within-block variability of grapevine vigor was largely controlled by variability in soil classes, and that carefully collected EMI and NDVI datasets can be exceedingly helpful for providing quantitative estimates of vineyard soil and vigor variability, as well as their covariation. The method is expected to be transferable to other viticultural regions, providing an approach to use easy-to-acquire, high resolution datasets to guide viticultural practices, including routine management and replanting.