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At least 505 records · Page 28

In Situ Identification of NNH and N 2 H 2 by Using Molecular-Beam Mass Spectrometry in Plasma-Assisted Catalysis for NH 3 Synthesis

In this work, ammonia synthesis at 533 K and atmospheric pressure was investigated in a coaxial dielectric barrier discharge (DBD) plasma reactor without packing and with porous γ-Al 2 O 3 , 5 wt % Ru/γ-Al 2 O 3 , or 5 wt % Co/γ-Al 2 O 3 catalyst particles. Gas-phase species were monitored in situ using an electron impact molecular-beam mass spectrometer (EI-MBMS). Gas-phase species NNH and N 2 H 2 were first identified under common conditions of plasma-assisted ammonia synthesis and were present at levels comparable to that of NH 3 in the plasma discharge. Concentrations of NNH, N 2 H 2 , and NH in a reactor packed with γ-Al 2 O 3 or other particles were lower than those observed in an empty reactor, while the concentration of NH 3 increased. These observations point to the importance of NNH and N 2 H 2 in plasma-assisted surface reactions in ammonia synthesis. Reaction pathways of direct adsorption of gas-phase NNH and N 2 H 2 on solid surfaces and subsequent reactions were proposed. This study demonstrated that in situ identification of gas-phase species via EI-MBMS provides a powerful approach to study the kinetics of plasmaassisted catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Visualization of Li-Whisker with Grating-Interferometry-Based Tricontrast X-ray Microtomography

The lithium-ion battery has demonstrated tremendous economic and social impacts. Upon battery operation under different conditions, lithium changes its chemical state and physical formation, leading to undesired side reactions, e.g., lithium dendrite growth that degrades the cell performance and causes safety concerns. In situ detection and visualization of lithium metal in functional batteries could offer insights with both scientific and industrial significance but remain a frontier challenge. In this work, we demonstrate in situ three-dimensional imaging of lithium whisker using a grating-interferometry-based tricontrast X-ray microtomography method. Our approach explicitly reveals the micromorphology of the electrochemically developed porous lithium whisker with micrometer-level spatial resolution while offering sensitivity to the nanoporosity that is smaller than the nominal resolution limit. Our result reveals valuable structural information on the lithium whisker that is otherwise inaccessible. This method is also readily applicable to a broad range of battery research, including all-solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Structural Evolution of Single Atom Catalysts during Electrochemical CO 2 Reduction by in Situ X-ray Absorption Spectroscopy

Investigating the structural variation of single-atom catalysts (SACs) is crucial to reveal the reaction mechanism under working conditions. Different in situ techniques, especially X-ray absorption spectroscopy (XAS), have been reported to study the structural changes in active sites. However, a systematic study of the relationship between the coordination environment and the catalytic ability of different kinds of SACs is still lacking. Herein, we established isolated transition metal atoms (Fe, Co, Ni, Cu) on N-doped carbon (M-N-C) and employed them in electrocatalytic CO 2 reduction reaction (CO 2 RR). Significantly, Ni-N-C exhibits the highest selectivity (similar to 97.9%) toward CO at -0.8 V vs RHE. In situ XAS characterization discloses the coordination number dependent catalytic performance. Further, the decreased average coordination number of Ni in Ni-N-C at the voltage point with maximum Faradaic efficiency was observed. Density functional theory further provides the possible mechanism of CO 2 -to-CO over the undercoordinated Ni-N-C structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and Mechanical Analysis of Individual Mineralized Collagen Fibrils Using In Situ Transmission Electron Microscopy

Bone serves as an example of nature’s architectured material with its characteristic blend of strength and toughness, all at a lightweight design. Given the hierarchical nature of these materials, it is essential to understand the governing mechanisms and organization of their constituents across length scales for bioinspired structural design. Despite recent advances in transmission electron microscopy (TEM) that have allowed us to witness the hierarchical arrangement of bone at micro-down to the nanoscale, we are still missing the details about the structural organization and mechanical properties of the main building blocks of bone─mineralized collagen fibrils (MCFs). Here, we present a method to extract individual MCFs from nature’s model material, mineralized turkey leg tendon, using a dropcasting procedure. By isolating the MCFs onto TEM supporting grids, we visualized the arrangement of organic and mineral phases within individual MCFs at the nanoscale. Using a four-dimensional scanning transmission electron microscopy (4D-STEM) approach, the orientation of individual mineral crystals within the MCFs was examined. Furthermore, we conducted in situ tensile experiments, revealing exceptional tensile strains of at least 8%, demonstrating the intricate relationship between structural organization and the mechanical behavior of MCFs. These insights into the ultrastructure of mineralized tissue building blocks, as well as the proposed sample-extraction method compatible with in situ mechanical testing, provide a strong basis for research into nature-inspired material design.

4D-STEM↗

Structural Reorganization of Noncellulosic Polymers Observed In Situ during Dilute Acid Pretreatment by Small-Angle Neutron Scattering

Production of second-generation bioethanol from lignocellulosic biomass requires pretreatment to open the plant cell wall structure and improve enzyme access. Many different thermochemical pretreatments have been extensively developed and employed, but the exact nature of plant cell wall recalcitrance and the most efficient and economical approach to alter plant cell wall structure via pretreatment still remain elusive. In order to understand the role of noncellulosic switchgrass polymers on the overall efficiency of pretreatment, the structural evolution of the noncellulosic polymers of the plant cell wall were investigated during dilute acid pretreatment (DAP) by employing in-situ small-angle neutron scattering (in-situ SANS). In this study, we observed real-time structural changes not possible to observe by any other technique. To deconvolute the structural evolution of lignin and hemicellulose polymers during DAP, native switchgrass (NATV), and isolated holocellulose (HOLO) and cellulose (CELL) fractions from NATV were studied. Our results show that aggregate particles first appear around 80 °C for NATV and HOLO samples. Further, due to the low temperature and pretreatment severity condition, these particles are likely derived from hemicellulose. The formations of much larger aggregate particles, only observed in the NATV sample, were attributed to lignin. For the HOLO sample, as the temperature and pretreatment severity condition increased, hemicellulose-derived aggregate particle sizes increased, suggesting this process was the nucleation and early stage formation of pseudolignin particles. Consistent with our interpretation of structural evolutions in NATV and HOLO samples, no formation of aggregate particles was observed in CELL samples for the entire duration of the pretreatment. These results suggest that not only lignin but also hemicellulose can form aggregate particles within plant cell walls during pretreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

N and OH-Immobilized Cu 3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO 2 Electromethanation in Bicontinuous Mesochannels

Cu-based catalysts hold promise for electrifying CO 2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO 2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites’ atomic-scale structures and engineering the carbon support’s mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO 2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu 3 (N,OH-Cu 3 ) clusters derived from atomically dispersed Cu–N 3 sites under realistic CO 2 reduction conditions. The N,OH-Cu 3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO 2 -to-CH 4 reduction compared to the C–C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H 2 O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO 2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu 3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO 2 reduction to methane at an industry-level current density of 300 mA cm –2 . In conclusion, this work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. Here, we used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Insights into Enhanced Cooperative Ligand Exchange Kinetics via Solvent-Induced Restacking in a 2D Metal–Organic Framework

Understanding the reaction kinetics at catalytically active sites is crucial for integrating catalytic two-dimensional (2D) materials into industrial processes. This study focuses on in situ observation of ligand exchange kinetics and solvent-assisted structural restacking transition in the 2D paddle wheel-based MOF [Cu 2 (dttc) 2 ] n (DUT-134(Cu), dttc = dithieno[3,2-b:2′,3′- d]thiophene-2,6-dicarboxylate). The ligand exchange process, involving the replacement of dimethylformamide (DMF) with nitriles such as acetonitrile (ACN), pentanenitrile, and heptanenitrile, was investigated using advanced in situ characterization techniques with high temporal resolution, including powder X-ray diffraction and Raman spectroscopy. The larger analytes exhibited reduced exchange rates, consistent with enhanced steric hindrance and greater diffusion constraints. Interestingly, the study revealed that the exchange of DMF with ACN induces a structural transition to higher symmetry within few seconds, a transition from AB to AA stacking mode of the layers, and a widening of the interlayer distance. Crucially, this structural transition dramatically accelerates the solvent exchange process through cooperative effects, offering critical advantages for catalytic applications. Notably, the reverse exchange from ACN to DMF proceeds more slowly and does not reverse the structural changes, but a new phase is formed with preserved AA stacking. By isotope labeling of linker molecules in combination with two complementary theoretical vibrational simulation methods, the precise assignment of Raman bands and the vibrational modes associated with the ligand exchange process could be achieved. These pioneering insights into the dynamic behavior of 2D MOFs, coupled with ligand exchange, establish a highly promising and transformative approach to achieving enhanced tunability and responsiveness in future catalytic applications.

Layers↗

High-Rate, Selective Electrosynthesis of Cyclohexanone Oxime via In Situ Generation and Release of Hydroxylamine on Bismuth

Oxime compounds are key industrial intermediates for nylon precursors and commodity chemicals. However, conventional routes rely on multistep reactions and hydroxylamine (NH 2 OH) salts, raising significant safety and sustainability concerns. Although electrosynthesis offers an alternative, oxime formation on d-block transition metals suffers from poor selectivity, as nitrogen oxyanion intermediates bind strongly to the surface and are readily over-reduced to ammonia. Here, we report morphology-controlled p-block bismuth rhombic dodecahedra (Bi RDs) that promote in situ NH 2 OH generation and its desorption into the electrolyte, enabling an electrochemical-chemical decoupled route for cyclohexanone oxime (CHO) synthesis. Bi RDs deliver nearly 100% Faradaic efficiency (FE) at −0.5 V vs. RHE and a yield of 1.4 mmol h –1 cm –2 at −0.9 V vs. RHE in an H-cell, while maintaining a CHO selectivity of nearly 100% at 100 mA cm –2 in a flow cell. Under identical conditions, d-block electrodes (Cu, Pd, Ag) show FE below 30%. Density functional theory calculations reveal that Bi 6p orbital-derived surface states weaken intermediate binding and facilitate NH 2 OH desorption, suppressing over-reduction. Kinetic analysis, post-addition trapping experiments, and in situ ATR-FTIR and Raman spectroscopy suggest the following reaction mechanism: NH 2 OH is selectively generated at the electrode surface, released as a freely diffusing intermediate, and undergoes homogeneous condensation with cyclohexanone in the bulk electrolyte, bypassing the surface-confined Langmuir–Hinshelwood pathway. These findings demonstrate that regulating intermediate desorption through p-block orbital chemistry provides a general strategy for achieving high selectivity in electro-organic nitrogen synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation and Optimization of Snow Albedo Scheme in Noah-MP Land Surface Model Using In Situ Spectral Observations in the Colorado Rockies

The Biosphere-Atmosphere Transfer Scheme (BATS) ground snow albedo algorithm is commonly used in land-surface models (LSM), weather forecasting and research applications. This study addresses key uncertainties in BATS simulated ground snow albedo within the Noah-MP LSM framework through evaluation and optimization of the Noah-MP BATS ground snow albedo formulation using 2-band (visible and near-infrared (NIR)) in situ albedo observations at Rocky Mountain field stations. The Noah-MP BATS ground snow albedo scheme is extremely sensitive to its input parameters. Namely, an ensemble generated by varying BATS input parameters within potentially plausible ranges provides an average daily range (maximum ensemble member minus minimum ensemble member) of ground snow albedo exceeding 0.45 in visible and NIR bands. Parameter optimization improves agreement between simulated and in situ observed ground snow albedo in visible, NIR and broadband spectrums. Importantly, optimized parameters result in reduced biases relative to observed fresh-snow albedo and better agreement with observed albedo decay. Our analysis across different sites supports that the optimized BATS ground snow albedo parameters are appropriate to transfer in space and time, at least within the region studied (the central-southern Rocky Mountains). The primary error source remaining after parameter optimization is that observed fresh-snow albedo is highly variable, particularly in the NIR spectrum, whereas BATS fresh-snow albedo is constant, an issue which requires further investigation. This study shows significant correlations between observed fresh-snow albedo and surface meteorological conditions (e.g., downward shortwave radiation and temperature) which can support future model development that attempts to include a time-varying formulation for fresh-snow albedo.

54 ENVIRONMENTAL SCIENCES↗

Enabling “lithium-free” manufacturing of pure lithium metal solid-state batteries through in situ plating

Abstract The coupling of solid-state electrolytes with a Li-metal anode and state-of-the-art (SOA) cathode materials is a promising path to develop inherently safe batteries with high energy density (>1000 Wh L −1 ). However, integrating metallic Li with solid-electrolytes using scalable processes is not only challenging, but also adds extraneous volume since SOA cathodes are fully lithiated. Here we show the potential for “Li-free” battery manufacturing using the Li 7 La 3 Zr 2 O 12 (LLZO) electrolyte. We demonstrate that Li-metal anodes >20 μm can be electroplated onto a current collector in situ without LLZO degradation and we propose a model to relate electrochemical and nucleation behavior. A full cell consisting of in situ formed Li, LLZO, and NCA is demonstrated, which exhibits stable cycling over 50 cycles with high Coulombic efficiencies. These findings demonstrate the viability of “Li-free” configurations using LLZO which may guide the design and manufacturing of high energy density solid-state batteries.

25 ENERGY STORAGE↗

In situ observation of thermal-driven degradation and safety concerns of lithiated graphite anode

Abstract Graphite, a robust host for reversible lithium storage, enabled the first commercially viable lithium-ion batteries. However, the thermal degradation pathway and the safety hazards of lithiated graphite remain elusive. Here, solid-electrolyte interphase (SEI) decomposition, lithium leaching, and gas release of the lithiated graphite anode during heating were examined by in situ synchrotron X-ray techniques and in situ mass spectroscopy. The source of flammable gas such as H 2 was identified and quantitively analyzed. Also, the existence of highly reactive residual lithium on the graphite surface was identified at high temperatures. Our results emphasized the critical role of the SEI in anode thermal stability and uncovered the potential safety hazards of the flammable gases and leached lithium. The anode thermal degradation mechanism revealed in the present work will stimulate more efforts in the rational design of anodes to enable safe energy storage.

25 ENERGY STORAGE↗

In situ infrared nanospectroscopy of the local processes at the Li/polymer electrolyte interface

Solid-state batteries possess the potential to significantly impact energy storage industries by enabling diverse benefits, such as increased safety and energy density. However, challenges persist with physicochemical properties and processes at electrode/electrolyte interfaces. Thus, there is great need to characterize such interfaces in situ, and unveil scientific understanding that catalyzes engineering solutions. To address this, we conduct multiscale in situ microscopies (optical, atomic force, and infrared near-field) and Fourier transform infrared spectroscopies (near-field nanospectroscopy and attenuated total reflection) of intact and electrochemically operational graphene/solid polymer electrolyte interfaces. We find nanoscale structural and chemical heterogeneities intrinsic to the solid polymer electrolyte initiate a cascade of additional interfacial nanoscale heterogeneities during Li plating and stripping; including Li-ion conductivity, electrolyte decomposition, and interphase formation. Moreover, our methodology to nondestructively characterize buried interfaces and interphases in their native environment with nanoscale resolution is readily adaptable to a number of other electrochemical systems and battery chemistries.

42 ENGINEERING↗

Radionuclide tracing based in situ corrosion and mass transport monitoring of 316L stainless steel in a molten salt closed loop

In the study, we report an in situ corrosion and mass transport monitoring method developed using a radionuclide tracing technique for the corrosion study of 316L stainless steel (316L SS) in a NaCl–MgCl 2 eutectic molten salt natural circulation loop. This method involves cyclotron irradiation of a small tube section with 16 MeV protons, later welds at the hot leg of the molten salt flow loop, generating radionuclides 51 Cr, 52 Mn, and 56 Co at the salt–alloy interface. By measuring the activity variations of these radionuclides at different sections along the loop, both the in situ monitoring of the corrosion attack depth of 316L SS and corrosion product transport and its precipitation in flowing NaCl–MgCl 2 molten salt are achieved. While 316L SS is the focus of this study, the technique reported herein can be extended to other structural materials being used in a wide range of industrial applications.

36 MATERIALS SCIENCE↗

In-situ probing of the Fischer-Tropsch reaction on Co single crystal surfaces up to 1 bar

The surface chemistry of the Fischer-Tropsch catalytic reaction over Co has still several unknows. Here, we report an in-situ X-ray photoelectron spectroscopy study of Co$(0001)$ and Co$(10\bar{1}4)$, and in-situ high energy surface X-ray diffraction of Co$(0001)$ during the Fischer-Tropsch reaction at 0.15 bar - 1 bar and 406 K - 548 K in a H 2 /CO gas mixture. We find that these Co surfaces remain metallic under all conditions and that the coverage of chemisorbed species ranges from 0.4–1.7 monolayers depending on pressure and temperature. The adsorbates include CO on-top, C/-C x H y and various longer hydrocarbon molecules, indicating a rate-limiting direct CO dissociation pathway and that only hydrocarbon species participate in the chain growth. The accumulation of hydrocarbon species points to the termination step being rate-limiting also. Furthermore, we demonstrate that the intermediate surface species are highly dynamic, appearing and disappearing with time delays after rapid changes in the reactants’ composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically in situ formed rocksalt phase in titanium dioxide determines pseudocapacitive sodium-ion storage

Earth-abundant TiO 2 is a promising negative electrode for low-cost sodium-ion batteries (SIBs) owing to its high capacity, rapid (dis)charging capability, safe operation potential and nonflammability. Crystalline anatase TiO 2 is not suitable for reversible Na + (de)intercalation, but it displays pseudocapacitive response after repeated cycles. Herein, we find and demonstrate that ordered rocksalt (RS) NaTiO 2 nanograins are in situ formed by electrochemically cycling with Na + ions in anatase and amorphous TiO 2 . The in situ formed RS-NaTiO 2 follows a solid-solution reaction with small volume changes of only 2.0%, that determines the pseudocapacitive “mirror-like” cyclic voltammetry curve with a couple of broad redox peaks at 0.75 V vs. Na + /Na, a high capacity of 253 mAh g −1 , high-rate capability and thousands of stable cycles. The multistep crystalline-to-amorphous-to-RS transformations are able to be electrochemically activated during the aging process of assembled full cells. Our finding provides a direction for developing unconventional Ti-based high-performance active materials for SIBs with both high energy and power densities.

Tang, Dafu [Xiamen University (China); Innovation ↗

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↗

Annealing of ion tracks in apatite under pressure characterized in situ by small angle x-ray scattering

Fission track thermochronology is routinely used to investigate the thermal history of sedimentary basins, as well as tectonic uplift and denudation rates. While the effect of temperature on fission track annealing has been studied extensively to calibrate the application of the technique, the effect of pressure during annealing is generally considered to be negligible. However, a previous study suggested elevated pressure results in a significantly different annealing behaviour that was previously unknown. Here, we present a method to study track annealing in situ under high pressure by using synchrotron- based small angle x-ray scattering (SAXS). To simulate fission tracks in a controlled environment, ion tracks were created in apatite from Durango, Mexico using 2 GeV Au or Bi ions provided by an ion accelerator facility. Samples were annealed at 250°C at approximately 1 GPa pressure using diamond anvil cells (DAcs) with heating capabilities. Additional in situ annealing experiments at ambient pressure and temperatures between 320 and 390°C were performed for comparison. At elevated pressure a significantly accelerated annealing rate of the tracks was observed compared with annealing at ambient pressure. However, when extrapolated to geologically relevant temperatures and pressures, the effects become very small. The measurement methodology presented provides a new avenue to study materials behaviour in extreme environments.

58 GEOSCIENCES↗