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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Mechanics of pore array collapse and interaction in shock-compressed polymethyl methacrylate (PMMA)

Recent studies on dynamic pore collapse have revealed significant development of shear localization, which can lead to material failure in porous structures and hot spot generation in energetic materials. These findings have dramatically improved the understanding of failure mechanisms during pore collapse but also prompt further investigation of realistic porous materials. In particular, porous media consist of many pores and porous networks. Even in low-porosity materials, pores can form in close proximity during the manufacturing process, leading to the critical question of pore–pore interaction during collapse under dynamic loading conditions. This study investigates, via plate impact experiments coupled with high-speed internal digital image correlation and shadowgraphy techniques, the collapse of two pores in shock-compressed PMMA at stresses between 0.4 and 1 GPa. The results of these experiments provide new insights into shear localization in pore collapse, in addition to distinct interactions between pores. Shadowgraphy measurements reveal novel, direct visualization of shear band development and crack evolution from pore surfaces. Spacing between adiabatic shear bands is measured over a range of impact stresses and is predicted accurately by the Grady–Kipp model. Pore interactions are found to effect a transition in the impact stress threshold at which different failure mechanisms initiate and are also found to possibly influence preferential sites for shear cracking. Throughout the study, numerical and theoretical models are leveraged to understand shear localization behavior. The role of baroclinicity and wave interactions between the pores is used to elucidate interaction mechanisms between pores.

Lawlor, Barry P. [California Institute of Technolo↗
DOE OSTI2022

TEAMER: DAISY Flow-noise Testing (Abstract)

Evaluating impacts of marine energy devices is generally difficult given the dynamic environment where these devices need to be placed. The University of Washington’s (UW) DAISY (The Drifting Acoustic Instrumentation SYstem) is designed to measure radiated noise around marine energy converters operating in energetic waves and currents. In currents, a primary limitation for measurement fidelity at low frequencies (< 100 Hz) is the potential for non-propagating “flow-noise” to mask propagating sound and inflate estimates of the radiated noise from marine energy converters at frequencies that overlap with hearing sensitivities of fish and some marine mammals. While free-drifting measurements help to minimize the relative velocity that produces flow-noise, significant levels were still observed during initial DAISY tests. This motivated the development of a fabric “flow shield” around the hydrophone that disrupts both flow-noise generation mechanisms proposed by the initial tests. First, the flow shield is a source of substantial drag which keeps the hydrophone package moving with the approximate velocity of the surrounding water, compensating for differential wind or current forcing on the surface expression. By minimizing relative velocity around the hydrophone, turbulence shed by the hydrophone is also minimized. Second, the flow shield creates a largely quiescent pocket around the hydrophone, minimizing advection of free stream turbulence over the hydrophone element. Field data collected in these experiments will test effectiveness of these flow shields and provide quantitative data use and deployment.

16 TIDAL AND WAVE POWER↗
DOE OSTI2023

Representation of the Convectively Coupled Kelvin Waves in Modern Reanalysis Products

Abstract This study aims to deepen our understanding of the destabilization mechanisms and the mean-state modulation of the convectively coupled Kelvin waves (CCKWs) while testing simple models for CCKWs. We examine CCKW precipitation, vertical structure, and energetics in four modern reanalyses: the fifth version of ECMWF Reanalysis (ERA5), NASA Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2), the second version of the NCEP Climate Forecast System Reanalysis (CFSR), and the Japanese 55-year Reanalysis (JRA-55). The CCKW precipitation signal strength in the wavenumber–frequency domain and the geographical distribution of CCKW precipitation variability are reasonably represented in all reanalyses, although they commonly underestimate the amplitude of CCKW precipitation. Despite considerable interreanalysis differences in the vertical structure of temperature and diabatic heating anomalies, the eddy available potential energy (EAPE) generation within the CCKWs is found to be associated with the second baroclinic mode whereas the first baroclinic mode damps CCKW EAPE in three out of four reanalyses. Geographically, strong CCKW activity occurs in the areas of high mean-state sea surface temperature (SST), where the second mode EAPE generation is higher, mainly due to a stronger stratiform heating and a tighter wave–convection coupling. Our results are supportive of the simple models for CCKWs in which CCKWs are destabilized within the second baroclinic mode component.

Meteorology & Atmospheric Sciences↗
DOE OSTI2022

Study of the interplay between lower-order and higher-order energetic strain-gradient effects in polycrystal plasticity

in this report strain-gradient (SG) plasticity refers to a class of non-local theories in which gradients of plastic slip determine the storage of geometrically necessary dislocations, introducing a length-scale dependence in the mechanical behavior of crystalline materials, which is otherwise lacking in local theories. In this work, we incorporate lower-order (LO) and higher-order energetic (HOE) strain-gradient effects into a crystal plasticity fast Fourier transform (FFT)-based formulation to investigate the interplay of the length scale that each strain-gradient term introduces at the microscale, and the mechanical properties that result at the macroscale. For an applicable range of length scales, we consider two systems: a 1-D two-phase face centered cubic (FCC) laminate and a 3-D FCC polycrystal, and two uniaxial deformation modes: monotonic tension and cyclic tension–compression. We show that increases in the individual LO and HOE length scales increase the hardening rate and strength of the material, respectively. When combined, the strong LO hardening is less pronounced than the effect alone due to the lowering of the gradients due to the HOE microstress. We demonstrate that the LO and HOE hardening manifest as “isotropic” (yield surface expansion) and “kinematic” (yield surface shift) effects, respectively, consistent with their theoretical origins. We show that in cyclic loading, the Bauschinger effect emerges in both local and non-local calculations and link its origins and severity to the behavior in the strain field, slip-system rates, and the HOE microforce.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Precise Colloidal Plasmonic Photocatalysts Constructed by Multistep Photodepositions

Natural photosynthesis relies on a sophisticated charge transfer pathway among multiple components with precise spatial, energetic, and temporal organizations in the aqueous environment. It continues to inspire and challenge the design and fabrication of artificial multicomponent colloidal nanostructures for solar-to-fuel conversion. Herein, we introduce a plasmonic photocatalyst synthesized with colloidal methods with five integrated components including cocatalysts installed in orthogonal locations. The precise deposition of individual inorganic components on an Au/TiO 2 nanodumbell nanostructure is enabled by photoreduction and photo-oxidation, which selectively occurs at the TiO 2 tip sites and Au lateral sites, respectively. Under visible-light irradiation, the photocatalyst exhibited activity of oxygen evolution from water without scavengers. Here, we demonstrate that each component is essential for improving the photocatalytic performance. In addition, mechanistic studies suggest that the photocatalytic reaction requires combining the hot charge carriers derived from exciting both the d-sp interband transition and the localized surface plasmon resonance of Au.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Implications of increased spatial and trophic overlap between juvenile Pacific salmon and Sablefish in the northern California Current

Abstract Objective The study was designed to assess long-term variability in the distribution of juvenile Pacific salmon Oncorhynchus spp. and Sablefish Anoplopoma fimbria. The study also evaluated whether Sablefish and Pacific salmon shared food resources and looked to characterize Sablefish during an understudied period of their life cycle. Methods To meet the objectives, the study used data from 26 years of surface trawls conducted in Oregon and Washington coastal waters (1998–2023). Spatial–temporal models were used to measure changes in abundance and distribution of Pacific salmon and Sablefish along with covariates of ocean temperature. The study evaluated trophic characteristics of Pacific salmon and Sablefish from 2020 for differences. The temporal variation in size and diets of Sablefish were also analyzed, along with energy density of fish caught in 2020. Result The spatial–temporal model demonstrated that there has been a nearshore expansion of juvenile Sablefish over the past 26 years that was correlated with increased ocean temperature. The nearshore expansion of Sablefish resulted in increased spatial and trophic overlap with juvenile Pacific salmon. While feeding in nearshore waters, juvenile Sablefish demonstrated competitive feeding advantages over juvenile Pacific salmon during a critical phase of salmonid early marine life history. Juvenile Sablefish exhibited significant ontogenetic diet and energetic shifts, and even the smallest (68–80 mm fork length) were piscivorous. Conclusions If juvenile Sablefish numbers continue to increase relative to Pacific salmon, they could exert more competitive pressure, especially if food resources become limited. Pacific salmon may experience adverse effects from competition, regardless of whether or not juvenile Sablefish, which have recently expanded into nearshore waters, successfully recruit to the adult population.

Daly, Elizabeth A. (ORCID:0000000195334457)↗
DOE OSTI2021

Nonintuitive Surface Self-Assembly of Functionalized Molecules on Ag(111)

The fabrication of nanomaterials involves selfordering processes of functional molecules on inorganic surfaces. To obtain specific molecular arrangements, a common strategy is to equip molecules with functional groups. However, focusing on the functional groups alone does not provide a comprehensive picture. Especially at interfaces, processes that govern self-ordering are complex and involve various physical and chemical effects, often leading to unexpected structures, as we showcase here on the example of a homologous series of quinones on Ag(111). Naively, one could expect that such quinones, which all bear the same functionalization, form similar motifs. In salient contrast, our joint theoretical and experimental study shows that profoundly different structures are formed. Using a machine-learning-based structure search algorithm, we find that this is due to a shift of the balance of three antagonizing driving forces: adsorbate-substrate interactions governing adsorption sites, adsorbate-adsorbate interactions favoring close packing, and steric hindrance inhibiting certain otherwise energetically beneficial molecular arrangements. The theoretical structures show excellent agreement with our experimental characterizations of the organic/ inorganic interfaces, both for the unit cell sizes and the orientations of the molecules within. The nonintuitive interplay of similarly important interaction mechanisms will continue to be a challenging aspect for the design of functional interfaces. With a detailed examination of all driving forces, we are, however, still able to devise a design principle for self-assembly of functionalized molecules.

structure prediction↗
DOE OSTI2023

Isolation and phase-space energization analysis of the instabilities in collisionless shocks

We analyse the generation of kinetic instabilities and their effect on the energization of ions in non-relativistic, oblique collisionless shocks using a 3D-3V (three spatial with three velocity components) simulation by dHybridR, a hybrid particle-in-cell code. At sufficiently high Mach number, quasi-perpendicular and oblique shocks can experience rippling of the shock surface caused by kinetic instabilities arising from free energy in the ion velocity distribution due to the combination of the incoming ion beam and the population of ions reflected at the shock front. To understand the role of the ripple on particle energization, we devise a new instability isolation method to identify the unstable modes underlying the ripple and interpret the results in terms of the governing kinetic instability. We generate velocity-space signatures using the field–particle correlation technique to look at energy transfer in phase space from the isolated instability driving the shock ripple, providing a viewpoint on the different dynamics of distinct populations of ions in phase space. Together, the field–particle correlation technique and our new instability isolation method provide a unique viewpoint on the different dynamics of distinct populations of ions in phase space and allow us to completely characterize the energetics of the collisionless shock under investigation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Mapping the Perseus galaxy cluster with XRISM: Gas kinematic features and their implications for turbulence

We present extended gas kinematic maps of the Perseus cluster based on a combination of five new XRISM/Resolve pointings observed in 2025 with four performance verification datasets from 2024, totaling a net exposure of 745 ks. To date, Perseus remains the only cluster that has been extensively mapped out to ≃0.7 r 2500 by XRISM/Resolve, while simultaneously offering sufficient spatial resolution to resolve gaseous substructures driven by mergers and active galactic nucleus (AGN) feedback. Our observations cover multiple radial directions and a broad range of dynamical scales, enabling us to characterize the kinematic properties of the intracluster medium up to a scale of ∼500 kpc. In the measurements, we detected high-velocity dispersions (≃300km s −1 ) in the eastern region of the cluster that are spatially coincident with the extended X-ray surface brightness excess and correspond to a nonthermal pressure fraction of ≃7 − 13%. The velocity field outside the AGN-dominant region can be effectively described by a single, large-scale kinematic driver based on the velocity structure function, which statistically favors an energy injection scale of at least a few hundred kpc. The estimated turbulent dissipation energy is comparable to the gravitational potential energy released by a recent merger, implying a significant role of turbulent cascade in the merger energy conversion. In the bulk velocity field, we observed a dipole-like pattern along the east-west direction with an amplitude of ≃ ± 200 − 300 km s −1 , indicating rotational motions induced by the recent merger event. This feature constrains the viewing direction to ≃30° −50° relative to the normal of the merger plane. Our hydrodynamic simulations suggest that Perseus has experienced at least two energetic mergers since redshift z ∼ 1, the most recent of which is associated with the radio galaxy IC310, in agreement with recent SRG/eROSITA findings. This study showcases exciting scientific opportunities for future missions with high-resolution spectroscopic capabilities (e.g., HUBS, LEM, and NewAthena).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Investigation of the distribution of laser-induced damage precursors in etched grating sidewalls fabricated using inductively coupled plasma reactive-ion etching

Inductively coupled plasma reactive-ion etching for grating fabrication is explored with emphasis on the type and distribution of process-induced defects that can act as precursors to laser-induced damage initiation. To provide flexibility in the ability to perform a variety of material characterization methods, grating-like features with large pitch were fabricated in silica monolayers. The results indicate that the etch process introduces surface fluorine and subsurface carbon-containing contamination, which reduces the laser-induced damage threshold. The local relative concentrations of the laser-damage precursors introduced during the etch step of the manufacturing process were investigated using angle-resolved damage testing, taking advantage of the shift of the location of the peak electric-field intensity incident on the grating sidewall. The results suggest an increased level of etch-related defects near the base of the sidewall, with directly fluorinated silicon identified as the primary defect.

Dent, R. [Univ. of Rochester, NY (United States). ↗
DOE OSTI2022

Modelling the Alfvén eigenmode induced fast-ion flow measured by an imaging neutral particle analyzer

An imaging neutral particle analyzer (INPA) provides energy and radially resolved measurements of the confined fast-ion population ranging from the high-field side to the edge on the midplane of the DIII-D tokamak. In recent experiments, it was used to diagnose fast-ion flow in the INPA-interrogated phase-space driven by multiple, marginally unstable Alfvén eigenmodes (AEs). Here, the key features of this measured fast-ion flow are: (I) a fast-ion flow from q min and the injection energy (81 keV) towards lower energies and plasma periphery.(II) A flow from the same location towards higher energies and the plasma core, (III) a phase-space 'hole' at the injected energy and plasma core and (IV) a pile-up at the plasma core at lower energies (~60 keV). Ad hoc energetic particle diffusivity modelling of TRANSP significantly deviates from the observation. Comparably, a reduced modelling, i.e. a combination of NOVA-K and ASCOT5 code with the measured mode structure and amplitude, generally reproduce some key features of the observed phase-space flow, but largely failed to interpret fast ion depletion near the plasma axis. At last, self-consistent, first-principle multi-phase hybrid simulations that include realistic neutral beam injection and collisions are able to reproduce most features of the time-resolved phase-space flow. During consecutive hybrid phases, an RSAE consistent with the experiment grows and saturates, redistributing the injected fast ions. The resulting synthetic INPA images are in good agreement with the measurement near the injection energy. The simulations track the fast-ion redistribution within the INPA range, confirming that the measured fast-ion flow follows streamlines defined by the intersection of phase-space surfaces of constant magnetic moment μ and constant E' = nE + ωP φ , where n and ω are the instability toroidal mode number and frequency, and E and P φ the ion energy and toroidal canonical momentum. Nonperturbative effects are required to reproduce the depletion of fast ions near the magnetic axis at the injection energy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Epitaxial growth of hexagonal BaNi O 3–δ thin films on SrTi O 3 (111) substrates

Transition metal oxides containing nickel species in oxidation states higher than 3+ often exhibit high catalytic activity, which makes them promising for applications as advanced electrocatalysts for water splitting and fuel cells. Here, we examine the structure and properties of BaNiO 3 (BNO) thin films, containing formally Ni 4+ , grown on SrTiO 3 (111) substrates using oxygen-plasma–assisted molecular beam epitaxy. X-ray diffraction and scanning transmission electron microscopy measurements reveal that BNO films have a hexagonal structure with $c$- and $a$-axes of mixed textures showing epitaxial relationships BNO (0001) ∥ SrTiO 3 (111) and BNO (10$\overline{1}$0) ∥ SrTi O 3 (111), respectively. The formation of the $a$-axis texture is dominant due to the smaller lattice mismatch with the substrate. Here, density functional theory calculations confirm that the hexagonal BNO film with the $a$-axis texture is energetically more favorable than the competing $c$-axis texture. Detailed spectroscopy data analysis indicates that hexagonal BNO films contain mixtures of Ni 2+ , Ni 3+ , and Ni 4+ species, with Ni 4+ being dominant. Our study provides insights into stabilizing Ni 4+ in complex oxides, which is important for further exploration of the potential of materials containing Ni 4+ .

36 MATERIALS SCIENCE↗
DOE OSTI2023

Molecular Geometry and Electronic Structure of Copper Corroles

Copper corroles are known for their unique multiconfigurational electronic structures in the ground state, which arise from the transfer of electrons from the π orbitals of the corrole to the d-orbital of copper. While density functional theory (DFT) provides reasonably good molecular geometries, the determination of the ground spin state and the associated energetics is heavily influenced by functional choice, particularly the percentage of the Hartree–Fock exchange. Using extended multireference perturbation theory methods (XMS-CASPT2), the functional choice can be assessed. The molecular geometries and electronic structures of both the unsubstituted and the meso-triphenyl copper corroles were investigated. A minimal active space was employed for structural characterization, while larger active spaces are required to examine the electronic structure. The XMS-CASPT2 investigations conclusively identify the ground electronic state as a multiconfigurational singlet (S o ) with three dominant electronic configurations in its lowest energy and characteristic saddled structure. In contrast, the planar geometry corresponds to the triplet state (T o ), which is approximately 5 kcal/mol higher in energy compared to the S o state for both the bare and substituted copper corroles. Notably, the planarity of the T o geometry is reduced in the substituted corrole compared with that in the unsubstituted one. By analyzing the potential energy surface (PES) between the S o and T o geometries using XMS-CASPT2, the multiconfigurational electronic structure is shown to transition toward a single electron configuration as the saddling angle decreases (i.e., as one approaches the planar geometry). Despite the ability of the functionals to reproduce the minimum energy structures, only the TPSSh-D 3 PES is reasonably close to the XMS-CASPT2 surface. Significant deviations along the PES are observed with other functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Rippled shock propagation in a laser-driven target at multimegabar pressures

The evolution of non-uniform shocks produced by modulated laser irradiation or surface perturbations is relevant to studies of inertial confinement fusion and material properties at high-energy-density conditions. We present results from an experiment conducted at the OMEGA EP laser facility, where a 300 GPa shock was driven into a fused silica sample with pre-fabricated single-mode surface modulations. Using time-resolved optical velocimetry, we captured the continuous evolution of rippled shock motion, enabling a comprehensive mapping of the spatial amplitude history from formation to phase reversal in a single experiment. Initially, the ablation-driven shock inherits a fraction of the surface modulation amplitude from the sample, which subsequently grows before decaying, ultimately leading to the flattening of the rippled shock and a phase reversal. We find that two-dimensional inviscid hydrodynamic simulation of the experiment is able to qualitatively capture many aspects of the rippled shock evolution but over-predicts the initial amplitude growth. This experimental platform, capable of accommodating varying ripple wavelengths, lays the groundwork for a potential viscometry method at extreme pressures, where viscous effects manifest as differences in shock flattening times between rippled shocks of two distinct wavelengths propagating through the sample.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2020

Development of a Platform at the Matter in Extreme Conditions End Station for Characterization of Matter Heated by Intense Laser-Accelerated Protons

High intensity short-pulse lasers have made possible the generation of energetic proton beams, unlocking numerous applications in high energy density science. One such application is uniform and isochoric heating of materials to the warm dense matter (WDM) state. We have developed a new experimental platform to simultaneously create and probe warm dense matter at the Matter in Extreme Conditions (MEC) end station at the Linac Coherent Light Source (LCLS). The short pulse optical laser (delivering up to 1 J in 45 fs) and the ultra-bright LCLS x-ray laser with tunable frequency respectively deliver high power required to heat materials to WDM and precision-timed high-resolution x-rays to probe them. The laser-accelerated proton beam driven from a flat 1.5 μm Cu foil was first measured then directed to a secondary sample of Al or polypropylene, typically 300-400 μm away. The time evolution of the sample electron temperature was measured using streaked optical pyrometry, where we observed a peak temperature of 0.9 0.15 eV on the rear surface of an Al sample heated by the proton beam. Here, the simulations using the hybrid-PIC code LSP and the rad-hydro code HELIOS show that a measured proton beam can heat Al to approximately 4 eV and polypropylene to 1 eV if instead focused by a hemispherical Cu target. Through additional LSP simulations, we anticipate creating hotter warm dense matter states (20 eV) by increasing the laser energy to 10 J and keeping the other laser parameters fixed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗
DOE OSTI2023

Hydrogen in disordered titania: connecting local chemistry, structure, and stoichiometry through accelerated exploration

Hydrogen incorporation in native surface oxides of metal alloys often controls the onset of metal hydriding, with implications for materials corrosion and hydrogen storage. A key representative example is titania, which forms as a passivating layer on a variety of titanium alloys for structural and functional applications. These oxides tend to be structurally diverse, featuring polymorphic phases, grain boundaries, and amorphous regions that generate a disparate set of unique local environments for hydrogen. Here, we introduce a workflow that can efficiently and accurately navigate this complexity. First, a machine learning force field, trained on ab initio molecular dynamics simulations, was used to generate amorphous configurations. Density functional theory calculations were then performed on these structures to identify local oxygen environments, which were compared against experimental observations. Second, to classify subtle differences across the disordered configuration space, we employ a graph-based sampling procedure. Finally, local hydrogen binding energies and hopping kinetics are computed using exhaustive density functional theory calculations on representative configurations. Here, we leverage this methodology to show that hydrogen binding energetics are described by local oxygen coordination, which in turn is affected by stoichiometry, and form the basis of hopping kinetics and diffusion. Together these results imply that hydrogen incorporation and transport in TiO x can be tailored through compositional engineering, with implications for improving the performance and durability of titanium-derived alloys in hydrogen environments.

36 MATERIALS SCIENCE↗