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At least 91 records · Page 5

ToF-SIMS in material research: A view from nanoscale hydrogen detection

Hydrogen in materials has attracted tremendous interest as its incorporation leads to significant alterations in nanoscale structure, composition, and chemistry, impacting functional properties. It has also been integral to nuclear fusion reactors and is considered a future clean energy source. However, nanoscale characterization and manipulation of hydrogen in materials are challenging as only a selected few analytical techniques can readily detect hydrogen, among which time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a unique and powerful one due to its excellent detection limit along with decent depth and lateral resolutions. Here, in this review, we discuss, using selected examples, how to detect and quantify hydrogen in materials by ToF-SIMS and its impact on revealing the hydrogenation/protonation-induced novel functional states in different classes of materials. In addition, we present our protocols on sample preparation and experimental conditions optimization, allowing us to achieve the best possible results. Finally, we highlight future research directions that can lead to the discovery of novel functional states and ultimately provide a deeper understanding of scientific questions in materials science.

36 MATERIALS SCIENCE↗

Creep suppression and fatigue in bio-based composites manufactured via conventional and large format additive manufacturing processes

The emergence of novel extrusion-based additive manufacturing (AM) processes has prompted the development of new thermoplastic composite feedstocks, and broadening sustainability initiatives have driven the development of bio-based and recyclable material for AM feedstocks. Poly(lactic acid) (PLA) with wood flour (WF) is one composite system that has been demonstrated in numerous AM applications, as well as traditional processing methods (i.e., compression and injection molding); however, there has been a need to understand how the variation in processing methodology impacts the material performance of these bio-based feedstocks from a fundamental perspective, with particular emphasis on creep for an extended application use-life. Herein, PLA/WF is explored as a feedstock material for large format additive manufacturing (LFAM) and the performance of additively manufactured materials is compared to those produced via more traditional processing methods. It is also demonstrated that the addition of WF decreases the material’s coefficient of thermal expansion (CTE) while increasing its Young’s modulus, susceptibility to water uptake, and creep fatigue resistance. Essentially, the addition of 20 wt% WF results in a 92 % decrease in rubbery regime CTE while simultaneously resulting in a 14 % increase in modulus, 190 % increase in water uptake, and a 31 % decrease in residual strain after cyclic creep tests. The processing method was also found to play a large role in the final part performance, with the printed material increasing the crystallinity by 183 % and 214 % compared to its compression and injection molded counterparts. Furthermore, the porosity of printed samples increased by two orders of magnitude compared to samples prepared via traditional processing methods.

36 MATERIALS SCIENCE↗

Ionic Liquids in Analytical Chemistry: Fundamentals, Technological Advances, and Future Outlook

The development of new analytical methods most often focus on novel materials used to impart selectivity or sensitivity to the protocol. Ionic liquids (ILs) are a class of solvents that have been extensively explored as promising materials for various applications and continue to be explored due to their tunable physicochemical properties. These materials possess melting temperatures below 100 °C and can interact with analytes through a multitude of interactions afforded by their readily tunable chemical structure. These interactions include electrostatic, dispersive, hydrogen bonding, π–π, and dipolar interactions and can be modulated or strengthened based on the functional groups present within the chemical structure. ILs consist predominately of organic cations and either inorganic or organic anions, both of which can be functionalized with desired moieties. Common cation and anions found in IL chemical structures are presented in Figure 1. The unique polarity afforded by the ionic structure has also led to their increasing use in areas including sample preparation, chemical separations, electrochemistry, mass spectrometry, and spectroscopy.

Zeger, Victoria R. [Iowa State Univ., Ames, IA (Un↗

Open Specy 1.0: Automated (Hyper)spectroscopy for Microplastics

Microplastic spectral analysis is one of the most time-consuming processes in studying microplastic pollution, often requiring days per sample. Researchers are transitioning to automated batch and hyperspectral image analysis techniques to enhance efficiency. Open Specy, initially aimed at manual single-spectrum analysis, has now integrated automated methods. This updated version, Open Specy 1.0, introduces several new features, including two algorithms for automated processing (smoothing and particle compression), an extensive library containing over 40,000 open-source Raman and FTIR spectra, and two machine learning classifiers (logistic regression and k medoids) developed from this library. Furthermore, it includes a revamped user interface, an R package, and a benchmark data set for testing future advancements in automated techniques. Researchers evaluated various configurations for hyperspectral smoothing, particle identification, compression, and splitting, to achieve combined recovery rates between 50 and 150% particle counts, identities, and sizes with a coefficient of variation (CV) of less than 40% (the accredited standard). Mean absorbance times the standard deviation provided a consistent particle identification. Hyperspectral smoothing led to a 96% combined recovery rate and reduced variability (CV = 38%) compared to the 86% recovery (CV = 83%) of nonsmoothed controls. Additionally, compressing spectra for particles was significantly faster (>3x) and showed similar accuracy but with reduced variability than processing each pixel individually. Key challenges persist in automating spectral analysis, particularly in refining particle splitting algorithms, and improving identification routines to minimize false positives and negatives. In conclusion, new methods in sample preparation for better stabilization and dispersion of particles could overcome some of these issues.

13 HYDRO ENERGY↗

Advanced Method Optimization with Categorical and Constrained Continuous Parameters

Traditional approaches to analytical method optimization (e.g., univariate and “guess-and-check”) can be time-consuming, costly, and often fail to identify true optima within the parameter space. Previous work defined and implemented a generalized technique for method optimization for continuous method parameters, but a knowledge gap remains for the incorporation of categorical variables into these advanced method optimization schemes. This work presents and validates a generalized optimization approach that incorporates both continuous and categorical variables while also utilizing a multivariate, multiobjective optimization scheme with Karush–Kuhn–Tucker conditions to bound the optimization space to solutions within the physical limitations of the parameter space. Method optimization from a case study using GC–MS for the analysis of 11 analytical standards with objectives to minimize peak width and maximize peak height resulted in a 3 orders of magnitude improvement in the average peak height and a 2 orders of magnitude improvement in the average peak width compared to the least optimal (but reasonable) instrumental parameters utilized in this study. This approach to optimization allows for a customizable method optimization in which users can include both continuous and categorical variables to achieve objectives specific to their analytical goals. This approach significantly reduces the labor and cost associated with traditional method development approaches and can be applied in a variety of scientific fields across a range of laboratory techniques (e.g., instrument method development, sample preparation, and extraction techniques).

Amorphous materials↗

Enhanced Spatial Proteomics and Metabolomics from a Single Tissue Section Using MALDI-MSI and LCM-microPOTS Platforms

Spatially resolved mass spectrometry (MS)-based multi-omics workflows are becoming more utilized for revealing the complex biology that occurs within tissues. However, these approaches commonly require multiple independent tissue sections to analyze the metabolite and protein compositions of these samples. This poses a significant challenge in preserving cell- or region-specific molecular fidelity, as variations between tissue sections can compromise the accurate correlation of molecular data. Here, in this study, we developed workflows for comprehensive multi-omics profiling from a single tissue section (STS) using different MS modalities. We enhanced the functionality of an electrically insulated substrate by employing metal-assisted approaches that enabled both MS-based untargeted spatial metabolomics and proteomics from STS. This allowed metabolite imaging using matrix-assisted laser desorption/ionization-MS imaging (MALDI-MSI), without compromising it for subsequent proteome profiling with laser capture microdissection (LCM)-based technology. Specifically, implementing copper tape as a backing for polyethylene naphthalate (PEN) slides enabled the detection of >140 metabolites across a poplar root tissue section using MALDI-trapped ion mobility spectrometry time of flight (timsTOF)-MS. Afterwards, we detected 6,571 unique proteins from two distinct root regions by leveraging LCM technology coupled to our microdroplet based sample preparation approach. We also developed an alternative workflow utilizing gold-coated PEN substrates for imaging with MALDI-Fourier-transform ion cyclotron resonance (FTICR)-MS, which permitted the profiling of >170 metabolites and the identification of 6,542 unique proteins across a single poplar root tissue section. These results were comparable to using each assay independently without modifications. These approaches offer new opportunities for high-resolution molecular profiling of multiple omics-levels across biological tissues.

Veličković, Marija [Pacific Northwest National Lab↗

Calibration-free analysis of Li isotope ratios using laser ablation and laser absorption spectroscopy

We introduce a rapid, calibration-free, all-optical method for high-precision lithium isotope ratio measurements in solid materials using laser ablation combined with tunable laser absorption spectroscopy. A new asynchronous acquisition method is used to acquire time-resolved, high-resolution spectra of the 6Li and 7Li D1 and D2 transitions near 671 nm. Isotope ratios and atomic column densities are extracted from measured spectra via a physics-based fitting model including hyperfine structure. Under 1 Torr air, spectra recorded = 0.75 ms after plasma onset exhibit narrow linewidths corresponding to Doppler temperatures = 400 K, enabling resolution of the isotope peaks with high signal-to-noise ratios. Analysis of LiAlO2 samples with varying 6Li:7Li ratios demonstrates isotopic precisions of 0.6–1.7% for spectra acquired in 30 s. Isotope ratios determined from the spectral fits show accuracy within –0.3% to –1.7% of reference ICP-MS measurements without requiring calibration to external standards. By eliminating sample preparation and enabling spatially resolved isotopic mapping, this method offers a rapid analysis approach to lithium isotope determination in solid materials relevant to nuclear energy, safeguards, and geochemistry.

Phillips, Mark C.↗

Development of a Flow-through Cell for Ultrasonic Extraction (UE)─Single Particle (SP)─ICP-MS─an Approach for Nano/Microparticle Elemental and Isotopic Analysis

Nanotechnology is a salient part of the scientific landscape, and analytical approaches are rapidly evolving to enable small-scale characterization of nano- and microparticle compositions and impurities. Here, a flow-through sonicating cell was developed for direct particle extraction from a silicon wafer and integrated with an inductively coupled plasma–mass spectrometer (ICP-MS) for subsequent elemental and isotopic characterization of the released particles. Ultrasonic extraction (UE)─single particle (SP)─ICP-MS offers controlled particle mobilization from solid substrates and allows for increased sample throughput by eliminating the need for pre-extraction of particles and decreasing sample preparation steps. Coupling this device to an ICP-MS with a time-of-flight (TOF) mass analyzer, it is possible to distinguish unique isotopic compositions of the particles. Both tungsten and nickel isotopically tagged particles, which were deposited on Si wafers, are presented here with analysis via UE─SP─ICP-MS. This approach could support efforts in the fields of particle synthesis, nuclear safeguards and forensics, environmental monitoring, and semiconductor industries in which the detection of particles from substrates and wafers is critical.

Paul, Molly [ORNL] (ORCID:0009000009672055)↗

An In Situ , Automated High-Explosives Aging Method Utilizing Two-Dimensional Gas Chromatography–Mass Spectrometry

Understanding chemical changes that occur in high explosives as they age is of great importance to the safe employment and storage of these compounds. Traditional methods of aging high explosives even under accelerated aging conditions are time intensive with durations on the order of months to years. The nature of traditional aging analyses reduces each sample to a snapshot data point often separated widely in time, requiring many assumptions as to how the degradation products develop. Further complicating matters, several analytical techniques are typically employed for each sample analysis in order to ascertain an entire picture of the decomposition pathways. To address these shortcomings with existing methods, a new method of accelerated aging of high explosives utilizing comprehensive two-dimensional gas chromatography coupled to high-resolution mass spectrometry (GC × GC-HRMS) was developed using 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) as a model compound for method development. This in situ automated method reduces the time scale of aging to a matter of hours using the inlet of the GC × GC as the aging vessel. GC × GC in combination with HRMS allowed for the collection of both evolved gases and other decomposition products produced during the entire aging process in real time with HRMS providing far greater certainty in identification of explosives aging products. Additionally, this method allowed for a higher throughput of samples with greatly simplified sample preparation. Chemometric analysis of the GC × GC-HRMS data set via the alteration analysis (ALA) enabled discovery of statistically significant chemical changes providing insight into the variation of decomposition pathways with varying aging temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring Approaches for Accelerated Mass Spectrometric Detection of Fluorochemicals from Aqueous Solutions Using Indirect, Adsorbent-Facilitated Desorption Ionization

There is a growing need for rapid, low-cost analytical tools to screen water supplies for persistent contaminants. Due to their ubiquitous presence in the environment and their detrimental effects on human health, there is a public interest in widespread testing for perfluoroalkyl substances (PFAS). However, the most common methods for PFAS analysis can be time-intensive, requiring a preconcentration step followed by liquid chromatography–mass spectrometry (LC–MS), and are cost-prohibitive for most members of the public. To address these challenges, this study explores a novel method for rapid analysis of aqueous analytes by concentrating analytes on solid adsorbents and detecting them using mass spectrometric analysis via desorption ionization directly from the adsorbent surface. We demonstrate this general approach of indirect solution analysis (ISA) with desorption electrospray ionization (ISA-DESI) and laser desorption ionization (ISA-LDI). Various adsorbent materials were screened, including commercial mesoporous carbons, alumina, and metal–organic frameworks (MOFs). Using ISA-DESI, we consistently detect concentrations as low as 5–100 parts per trillion (ppt) for perfluorooctanoic acid (PFOA) and 10–100 ppt for perfluoroundecanoic acid (PFUnDA). This approach enables rapid detection in under 5 min, making it suitable for applications requiring trace detection with fast response times. We further demonstrate the use of ISA-DESI on a range of environmentally relevant contaminants. Advantages of this indirect solution analysis approach include simplified sample preparation, accelerated analysis, and low cost with readily available materials, making it a promising tool to accelerate mass spectrometric PFAS detection for identifying contaminated sites, performing laboratory studies, and monitoring industrial waste streams.

Bays, Nathan Robert [Sandia National Laboratories ↗

Synthesis of NiRu-Layered Double Hydroxide for Enhanced Oxygen Evolution Reaction

Nickel−ruthenium layered double hydroxide (NiRu-LDH) was synthesized by coprecipitation using formamide as both solvent and intercalant. The synthesis was performed at various temperatures to study the impact of temperature on electrochemical performance. Temperature plays a vital role in optimizing LDH synthesis to enhance oxygen evolution reaction (OER) efficiency. The optimal temperature yielded a well-defined morphology with balanced crystallinity, leading to more active sites and improved charge transfer. Electrochemical tests indicated that the NiRu-LDH sample prepared at 50 °C (NiRu-LDH-50) required only 280 mV overpotential versus the reversible hydrogen electrode to achieve 10 mA/cm 2 and exhibited a low Tafel slope of 52 mV/dec, demonstrating excellent catalytic kinetics. This study presents the synthesis of NiRu-LDH via coprecipitation and emphasizes how reaction temperature influences LDH structural properties and OER performance.

Catalysts↗

Evaluating Limits of Machine Learning-Assisted Raman Spectroscopy in Classification of Biological Samples

Machine learning (ML)-assisted Raman spectroscopy has become a powerful analytical tool for the classification and identification of analytes; however, technical challenges impacting its detection accuracy have not been thoroughly investigated. This study explores experimental factors affecting classification performance. Among the evaluated ML models, ML algorithms show minimal impact on classification accuracy. Instead, experimental factors, including spectral similarity between tested samples and data quality, dominate detection performance. Increases in spectral noise and spectral similarity significantly reduce classification accuracy. In well-controlled samples with low experimental noise, ML-assisted Raman spectroscopy can discriminate lipid mixtures with a composition difference of 1.85 mol %. To assess the effect of biological heterogeneity, we analyzed single-cell Raman spectra from Saccharomyces cerevisiae strains carrying single, double, or triple gene mutations. Intrinsic cell-to-cell variability introduced substantial spectral differences, severely reducing the accuracy of multiclass classification of these genetically similar strains at the single-cell level. Averaging Raman spectra across multiple cells improved classification accuracy by reducing this spectral variability. We also assess the effectiveness of transfer learning across different Raman spectrometers, specifically by applying an ML model trained on one instrument to another Raman spectrometer. Transfer learning can be improved with proper instrument calibration, highlighting the importance of instrument standardization. Overall, our results demonstrate that data quality and spectral similarity are the primary bottlenecks in ML-assisted Raman spectroscopy. Careful attention to sample preparation, data acquisition, measurement conditions, and instrument calibration is critical to achieving robust and reliable classification performance.

Fungi↗

Automated Calibration for Rapid Optical Spectroscopy Sensor Development for Online Monitoring

An automated platform has been developed to assist researchers in the rapid development of optical spectroscopy sensors to quantify species from spectral data. This platform performs calibration and validation measurements simultaneously. Real-time, in situ monitoring of complex systems through optical spectroscopy has been shown to be a useful tool; however, building calibration models requires development time, which can be a limiting factor in the case of radiological or otherwise hazardous systems. While calibration time can be reduced through optimized design of experiments, this study approached the challenge differently through automation. The ATLAS (Automated Transient Learning for Applied Sensors) platform used pneumatic control of stock solutions to cycle flow profiles through desired calibration concentrations for multivariate model construction. Additionally, the transients between desired concentrations based on flow calculations were used as validation measurements to understand model predictive capabilities. This automated approach yielded an incredible 76% reduction in model development time and a 60% reduction in sample volume versus estimated manual sample preparation and static measurements. The ATLAS system was demonstrated on two systems: a three-lanthanide system with Pr/Nd/Ho representing a use case with significant overlap or interference between analyte signatures and an alternate system containing Pr/Nd/Ni to demonstrate a use case in which broad-band corrosion species signatures interfered with more distinct lanthanide absorbance profiles. Both systems resulted in strong model prediction performance (RMSEP < 9%). Lastly, ATLAS was demonstrated as a tool to simulate process monitoring scenarios (e.g., column separation) in which models can be further optimized to account for day-to-day changes as necessary (e.g., baseline correction). Ultimately, ATLAS offers a vital tool to rapidly screen monitoring methods, investigate sensor fusion, and explore more complex systems (i.e., larger numbers of species).

47 OTHER INSTRUMENTATION↗

High-Throughput Discovery Illuminates Design Principles and Limits for Long-Lived Charged Species in Organic Electrolytes

The chemical stability of charged molecules in all-organic redox flow batteries (RFBs) is required for the prolonged operation of these devices. Molecular engineering and electrolyte optimization are used to mitigate parasitic reactions and extend the lifetimes of the charge carriers. However, how much can structural variation extend the lifetime? To probe this query, we designed a high-throughput kinetic study of the radical cation of N-methylphenothiazinium, guided by statistical sampling and learning algorithms. Using Argonne’s autonomous discovery facility, we conducted over 6,000 kinetic experiments with robotic sample preparation, parallel kinetic measurements, and machine learning inputs, testing 188 solvent molecules selected from a space of over 540 candidates from 11 chemical classes. Algorithmic selections guided us to stable solvent candidates, which were further tested in high concentration with and without supporting electrolyte. Our findings reveal the inherent difficulty of exceeding the current state of the art through solvent variation. The desired stability is statistically rare and poorly predictable. Among the many tested, only three solvents significantly outperformed our baseline, acetonitrile─and none by more than a factor of 3─suggesting a general challenge in achieving the necessary techno-economic targets. Furthermore, we suggest that self-discharge through solvent homolysis is the cause of the observed limitations. Several structural motifs contribute to >1,000 h half-life stability including molecular simplicity, symmetry, oxidation complement, and strategic fluorination. Importantly, this workflow establishes effective assays for diagnosing and predicting oxidative stress for highly stable liquid electrolytes in all batteries.

Batteries↗

Real-Time Screening for Uranium Enrichment by Paper Spray Ionization Mass Spectrometry for Field Applications

A rapid isotope ratio screening technique for uranium enrichment is demonstrated by utilizing paper spray ionization (PSI) high-resolution mass spectrometry (HRMS). Measurements were conducted using an ambient ionization mass spectrometer coupled to a custom-made JEOL PSI attachment apparatus, with de minimus sample preparation requirements. The current method detection limit for individual isotopes (e.g., 235 U and 238 U) is approximately 50 pg, with subsequent optimization expected to further improve U isotopic sensitivity. The PSI analytical method described herein can support rapid analysis (both in-field and in-lab screening) of isotopes-of-interest, as demonstrated by empirical differentiation of depleted uranium (DU) and low enriched uranium (LEU) analytical aliquots. Furthermore, this analytical workflow holds promise for applications in nuclear forensics, international nuclear safeguards, and nonproliferation missions.

Anions↗

Constraints and Drivers of Dissolved Fluxes of Pyrogenic Carbon in Soil and Freshwater Systems: A Global Review and Meta‐Analysis

Abstract Pyrogenic carbon (PyC) is a significant component of the global soil carbon pool due to its longer environmental persistence than other soil organic matter components. Despite PyC's persistence in soil, recent work has indicated that it is susceptible to loss processes such as mineralization and leaching, with the significance and magnitude of these largely unknown at the hillslope and watershed scales. We present a review of the work concerning dissolved PyC transport in soil and freshwater. Our analysis found that the primary environmental controls on dissolved PyC (dPyC) transport are the formation conditions and quality of the PyC itself, with longer and higher temperature charring conditions leading to less transport of dPyC. While correlations between dPyC and dissolved organic carbon in rivers and other pools are frequently reported, the slope of these correlations was pool‐dependent (i.e., soil‐water, precipitation, lakes, streams, rivers), suggesting site‐specific environmental controls. However, the lack of consistency in analytical techniques and sample preparation remains a major challenge to quantifying environmental controls on dPyC fluxes. We propose that future research should focus on the following: (a) consistency in methodological approaches, (b) more quantitative measures of dPyC in pools and fluxes from soils to streams, (c) turnover times of dPyC in soils and aquatic systems, and (d) improved understanding of how mechanisms controlling the fate of dPyC in dynamic post‐fire landscapes interact. With more refined quantitative information about the controls on dPyC transport at the hillslope and landscape scale, we can increase the accuracy and utility of global carbon models.

58 GEOSCIENCES↗

Imaging and spatially resolved mass spectrometry applications in nephrology

The application of spatially resolved mass spectrometry (MS) and MS imaging approaches for studying biomolecular processes in the kidney is rapidly growing. These powerful methods, which enable label-free and multiplexed detection of many molecular classes across omics domains (including metabolites, drugs, proteins and protein post-translational modifications), are beginning to reveal new molecular insights related to kidney health and disease. Further, the complexity of the kidney often necessitates multiple scales of analysis for interrogating biofluids, whole organs, functional tissue units, single cells and subcellular compartments. Various MS methods can generate omics data across these spatial domains and facilitate both basic science and pathological assessment of the kidney. Optimal processes related to sample preparation and handling for different MS applications are rapidly evolving. Emerging technology and methods, improvement of spatial resolution, broader molecular characterization, multimodal and multiomics approaches and the use of machine learning and artificial intelligence approaches promise to make these applications even more valuable in the field of nephology. Overall, spatially resolved MS and MS imaging methods have the potential to fill much of the omics gap in systems biology analysis of the kidney and provide functional outputs that cannot be obtained using genomics and transcriptomic methods.

60 APPLIED LIFE SCIENCES↗

Integrated fluorescence light microscopy-guided cryo-focused ion beam-milling for in situ montage cryo-ET

Cryogenic-electron tomography (cryo-ET) permits the in situ visualization of biological macromolecules at the molecular level. Owing to the variable thickness of cells, tissues and organisms, frozen specimens may need to be thinned by cryo-focused ion beam (FIB) milling to produce thin (<500 nm) cryo-lamellae suitable for cryo-ET. Locating regions of interest remains a challenge because untargeted milling can lead to inadvertent ablation and removal of regions of interest. Correlative light and electron microscopy, combined with cryo-FIB milling, can guide the identification of labeled targets in the cellular milieu. Multiple transfers between cryo-imaging instruments, cumbersome correlation algorithms, limited accuracy and low throughput have hindered the routine adoption of cryo-FIB milling within a multimodal correlative workflow for in situ structural biology. Here, in this study, we present a workflow for 3D correlative cryo-fluorescence light microscopy-FIB-ET that streamlines fluorescence light microscopy-guided FIB milling, improving throughput while preserving both structural and contextual information. The complete integration of hardware and software described here minimizes sample contamination from cross-platform exchanges and greatly enhances the efficiency of 3D targeting in cryo-milling. We then describe procedures for implementing montage parallel array cryo-ET (MPACT), which can be easily adapted to any modern life-science transmission electron microscope. MPACT supports high-throughput cryo-ET acquisitions (10 tilt series in 1.5 h) for structure determination and comprehensive contextual understanding of macromolecules within their native surroundings. A complete session from sample preparation to MPACT data processing takes 5−7 d for an individual experienced in both cryo-EM and cryo-FIB milling.

Yang, Jie E. [Univ. of Wisconsin, Madison, WI (Uni↗