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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Effect of Mg and Ni impurities on tritium diffusion in lithium ceramics through cluster dynamics simulations

This study investigates the impact of Mg and Ni doping on tritium diffusion in LiAlO 2 and LiAl 5 O 8 ceramics, that are used in tritium-producing burnable absorber rods (TPBARs). Utilizing Centipede simulations across a broad temperature range (500 K to 1250 K), we explore the interplay between defect dynamics, cluster formation, and tritium mobility. In LiAlO 2 , Mg doping significantly enhances tritium diffusivity by increasing tritium interstitial concentrations and diffusion coefficients of key species, thereby doubling the overall tritium diffusivity. Ni doping, while shifting the dominant defect to Li vacancies, maintains high tritium mobility due to the low binding energy of Li vacancy-tritium complexes, which ensures effective tritium migration. In LiAl 5 O 8 , Mg and Ni doping results in a slight reduction in the diffusion coefficients of key species, yet the dramatic increase in tritium interstitial concentrations compensates, leading to a net small increase in tritium diffusivity. In conclusion, the findings highlight the critical role of defects in tritium transport and the effect of Mg and Ni defects on the performance of these ceramics in demanding nuclear environments.

Cluster dynamics↗
DOE OSTI2025

First-principles investigation of cerium and neodymium diffusion in BCC chromium and vanadium via vacancy-mediated transport

Lanthanide transport plays a crucial role in the performance and longevity of metallic nuclear fuels. This study examines the diffusion behavior of Ce and Nd—two major fission products—in body-centered cubic (BCC) Cr and V, which are potential liner or coating materials for mitigating fuel-cladding chemical interactions (FCCI). Using density functional theory (DFT) calculations and self-consistent mean-field (SCMF) analysis, the vacancy-mediated diffusion coefficients are evaluated. Our findings reveal that Ce and Nd act as oversized solutes and are strongly bound to vacancies in BCC Cr and V, with diffusivities in Cr significantly lower than in V and in hexagonal closed-packed (HCP) Zr, as investigated in our previous work. The activation energies for Ce and Nd diffusion are 3.39 and 3.32 eV, respectively, in BCC Cr, and 2.56 and 2.33 eV, respectively, in BCC V. Analysis of vacancy drag and partial diffusion coefficient ratios indicates a strong tendency for lanthanide enrichment at vacancy sinks in BCC Cr, and to a lesser extent in BCC V, with this effect persisting up to the melting point in Cr and remaining substantial for Nd in V at high temperatures. Under irradiation, the increase in vacancy concentration is expected to enhance lanthanide transport, potentially accelerating interactions at liner-cladding interfaces. Although BCC Cr exhibits relatively low lanthanide diffusivities under equilibrium conditions, the expected segregation tendencies under irradiation suggest that Zr liners may be a more favorable option. Further investigations using rate theory, cluster dynamics, and phase-field modeling are required to quantitatively assess the performance of these materials in reactor environments.

36 - MATERIALS SCIENCE↗
DOE OSTI2015

Structure and ionic conductivity of well-aligned polycrystalline sodium titanogallate grown by reactive diffusion

We prepared the b-axis-oriented polycrystalline Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} (NTGO) embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix using the reactive diffusion technique. When the sandwich-type Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5} diffusion couple was heated at 1323 K for 24 h, the NTGO polycrystal was readily formed in the presence of a liquid phase. The resulting polycrystalline material was characterized by X-ray diffractometry, electron microscopy and impedance spectroscopy. We mechanically processed the annealed diffusion couple and obtained the thin-plate electrolyte consisting mostly of the grain-aligned NTGO polycrystal. The ionic conductivity (σ) of the electrolyte along the common b-axis direction steadily increased from 1.3×10{sup −4} to 7.3×10{sup −3} S/cm as the temperature increased from 573 to 1073 K. There was a slope change at ca. 792 K for the Arrhenius plot of σ; the activation energies were 0.39 eV above this temperature and 0.57 eV below it. The NTGO showed the crystal structure (space group C2/m) with substantial positional disordering of one of the two Ga sites. The Na{sup +} ions occupied ca. 43% of the Wyckoff position 4i site, the deficiency of which would contribute to the relatively high ionic conductivity along the b-axis. The reactive diffusion could be widely applicable as the novel technique to the preparation of grain-aligned ceramics of multi-component systems. - Graphical abstract: We have prepared the b-axis-oriented Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} polycrystal embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix by the heat treatment of sandwich-type diffusion couple of Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5}. The resulting Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} electrolyte showed the ionic conductivity ranging from 1.3×10{sup −4} S/cm at 573 K to 7.3×10{sup −3} S/cm at 1073 K. - Highlights: • The b-axis-oriented polycrystalline Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} is successfully prepared. • Crystal structure of Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} is determined by single-crystal XRD. • The polycrystal shows relatively high Na{sup +} ion conductivity along the common b-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tensile behavior of diffusion bonded AA6061 - AA6061 with variation in cooling method

Hot isostatically pressed AA6061 cladding is an important structural component of the high performance, Zr-laminated U-10Mo monolithic fuel system for the application in research and test reactors. In this study, the mechanical behavior of two diffusion bonded aluminum alloy, AA6061, was examined using tensile testing. Solid-to-solid diffusion bonding between two pieces of AA6061 was performed by isothermal annealing at 560 °C for 1.5 h, and diffusion couples were subsequently cooled via three different cooling methods: furnace cooling, air cooling, and water quenching. Dog-bone shaped tensile specimens, with 10 mm in gauge length (with diffusion bonded interface in the middle), and 1.5 × 1.5 mm 2 gauge cross-sections, were fabricated from the diffusion bonded AA6061 by electro-discharge machining. Yield strength (% EL at failure) of furnace cooled, air cooled and water quenched tensile specimens determined was 82 ~ 89 MPa (10 ~ 30%), 112 ~ 116 MPa (10 ~ 14%), and 149 ~ 164 MPa (10 ~ 17%), respectively. This variation in mechanical behavior was examined with cooling-rate dependent, concentrated precipitation of Mg 2 Si at the diffusion bonded interface, with due respect for mechanical properties of the AA6061 alloy that inherently vary as a function of cooling rate from 560 °C. Finite element analysis using ABAQUS was employed to augment experimental findings with the appropriate microstructural constituents and alloy properties. Results suggest that the strength is dominated by matrix/bulk properties of AA6061, while ductility is strongly influenced by the cooling method dependent presence of Mg 2 Si precipitates at the interface.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2014

Imaging Fluorescence-Correlation Spectroscopy for Measuring Fast Surface Diffusion at Liquid/Solid Interfaces

The development of techniques to probe interfacial molecular transport is important for understanding and optimizing surface-based analytical methods including surface-enhanced spectroscopies, biological assays, and chemical separations. Single-molecule-fluorescence imaging and tracking has been used to measure lateral diffusion rates of fluorescent molecules at surfaces, but the technique is limited to the study of slower diffusion, where molecules must remain relatively stationary during acquisition of an image in order to build up sufficient intensity in a spot to detect and localize the molecule. Although faster time resolution can be achieved by fluorescence-correlation spectroscopy (FCS), where intensity fluctuations in a small spot are related to the motions of molecules on the surface, long-lived adsorption events arising from surface inhomogeneity can overwhelm the correlation measurement and mask the surface diffusion of the moving population. Here, we exploit a combination of these two techniques, imaging-FCS, for measurement of fast interfacial transport at a model chromatographic surface. This is accomplished by rapid imaging of the surface using an electron-multiplied-charged-coupled-device (CCD) camera, while limiting the acquisition to a small area on the camera to allow fast framing rates. The total intensity from the sampled region is autocorrelated to determine surface diffusion rates of molecules with millisecond time resolution. Here, the technique allows electronic control over the acquisition region, which can be used to avoid strong adsorption sites and thus minimize their contribution to the measured autocorrelation decay and to vary the acquisition area to resolve surface diffusion from adsorption and desorption kinetics. As proof of concept, imaging-FCS was used to measure surface diffusion rates, interfacial populations, and adsorption–desorption rates of 1,1'-dioctadecyl-3,3,3'3'-tetramethylindocarbocyanine (DiI) on planar C18- and C1-modified surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Flux Equations for Osmotically Moderated Sorption–Diffusion Transport in Rigid Microporous Membranes

The development of non-aqueous reverse osmosis separations via the use of rigid microporous membrane materials suggests that flux equations originally developed for swellable polymeric membranes should be revisited. This paper demonstrates that the gradient of fractional occupancy of penetrant molecules within the micropores of the membrane is the driving force for permeation without requiring assumptions about pressure within the membrane. Flux equations are derived using both Fickian and Maxwell-Stefan approaches, and different behavior in the permeate flux versus upstream hydraulic pressure relationship is shown to arise as a result of differences in the loading dependence of the single component Maxwell-Stefan diffusivity. Molecular modeling results available in the literature and experimental data obtained from carbon molecular sieve (CMS) membranes showcase that these loading-dependent changes in the Maxwell-Stefan diffusivity are possible. This loading dependence is separated into three regimes: so-called “weak confinement” diffusion and “strong confinement” diffusion, both of which have been discussed at length in the literature, and a new “hybrid confinement” diffusion, which is introduced here. Furthermore, the separation mechanism of solvent molecules through a rigid bimodally microporous membrane is studied using xylene molecules passing through CMS membranes fabricated under different conditions as examples. Altogether, this study provides fundamental insight and guidance into osmotically-moderated sorption-diffusion transport of solvent molecules through rigid microporous membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM + ][TFSI – ]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340-1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ~1 solvent molecule. Finally, the scarcity of solvent–ion interactions explains the fact that the diffusivity of ions in the mixture significantly depends on the viscosity of the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

NMR and Theoretical Study of In-Pore Diffusivity of Ionic Liquid–Solvent Mixtures

We report despite having a lower energy density than common batteries, electric double-layer capacitors (EDLCs) offer several advantages for high-power applications, including high power density, quick charge and discharge time, and long cycle life. Room-temperature ionic liquids (RTILs) have been intensely studied as promising electrolytes for applications in ELDCs because of their wide potential window, low volatility, as well as thermal and chemical stability. The main deficiency of neat RTILs in such applications is the sluggish diffusivity, which restricts the EDLCs’ power density. To alleviate the slow diffusivity, RTILs can be used in a mixture with organic solvents. In this study, we applied two-dimensional exchange nuclear magnetic resonance spectroscopy (2D EXSY NMR) and molecular dynamics (MD) simulations to investigate the diffusivity of anions of an RTIL, namely, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMIM + –TFSI – ), dissolved in five different organic solvents, in the micropores of activated carbon. We determined that the relative concentrations of ions in solutions in the micropores were higher than those in the bulk solutions and were also solvent-dependent. The ion diffusivities in the pores were found to be almost 2 orders of magnitude slower than in the bulk solutions, with methanol showing the largest relative disparity. These results suggested that the interactions of solvents with the activated carbon are critical not only to the power density of EDLCs but also to the energy density. The comparisons of ion diffusivities between the experiments and the MD simulations suggest the need to consider also the surface functionalities of activated carbon for the simulation of ion diffusion in the micropores of activated carbon.

electric double layer capacitors↗
DOE OSTI2024

Adsorption and Solvation Modulate Rhodamine B Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

Confinement of solvents and solutes within nanoporous materials frequently leads to the emergence of unique mass transport behaviors that, once fully understood, may lead to improved chemical separations. Here, the diffusion of Rhodamine B (RhB) dye within 10 and 20 nm diameter anodic aluminum oxide (AAO) nanopores filled with binary ethanol/water mixtures is investigated. Mixture compositions spanning from pure ethanol to pure water are employed. The results of confocal fluorescence correlation spectroscopy studies reveal that RhB diffusion occurs by a two-component mechanism comprising composition-dependent fast and slow motions, characterized by diffusion coefficients D f and D s . The results are consistent with those of previous studies performed under more limited conditions [J. Phys. Chem. C, 2023, 127, 411-420]. The fast component scales with mixture viscosity and is assigned to hindered bulk-like diffusion in central pore regions. Slow diffusion likely involves adsorption of RhB to the pore surface and may be described by a desorption mediated mechanism. The occurrence of RhB adsorption to the AAO surface is verified at the single-molecule level by wide-field fluorescence imaging of membrane cross-sectional surfaces. Unique composition dependent trends in the autocorrelation amplitude and in D s that mimic bulk RhB solubility are revealed. D s is found to be smallest in pure ethanol and pure water and largest in intermediate mixtures. These results suggest that RhB surface adsorption is strongest in the pure liquids and weakest in mixtures of intermediate composition, where the dye is least soluble, and most soluble, respectively. As a result, molecular dynamics simulations reveal that a water layer appears on the pore surface under most conditions, while RhB is solvated primarily by ethanol. The composition dependence of RhB diffusion is concluded to reflect its solvation dependent interactions with the pore walls.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Transition State Theory Methods To Measure Diffusion in Flexible Nanoporous Materials: Application to a Porous Organic Cage Crystal

Transition state theory (TST) methods are useful for predicting adsorbate diffusivities in nanoporous materials at timescales inaccessible to molecular dynamics (MD). Most TST applications treat the nanoporous framework as rigid, which is inaccurate in highly flexible materials or where adsorbate dimensions are comparable to the size of pore aperatures. In this study, we demonstrate two computationally efficient TST methods for simulating adsorbate diffusion in nanoporous materials where framework flexibility has a significant influence on diffusion. These methods are applied to light gas diffusion in porous organic cage crystal 3 (CC3), a highly flexible molecular crystal that has shown promise in gas separation applications. Diffusion in CC3 is modeled as a series of uncorrelated adsorbate hops between cage molecules and the voids between adjacent cages. The first method we applied to compute adsorbate hopping rates in CC3 is implicit ligand sampling (ILS). In ILS TST, hopping rates are calculated in an ensemble of rigid framework snapshots captured from a fully flexible MD trajectory of the empty CC3 structure. The second TST method we applied is umbrella sampling (US), where hopping rates are computed from a series of biased MD simulations. Our ILS and US TST calculations are shown to agree well with direct MD simulation of adsorbate diffusion in CC3. We anticipate that the efficient TST methods detailed here will be broadly applicable other classes of flexible nanoporous materials such as metal–organic frameworks.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Machine Learning-Based Upscaling of Finite-Size Molecular Dynamics Diffusion Simulations for Binary Fluids

Molecular diffusion coefficients calculated using molecular dynamics (MD) simulations suffer from finite-size (i.e., finite box size and finite particle number) effects. Results from finite-sized MD simulations can be upscaled to infinite simulation size by applying a correction factor. For self-diffusion of single-component fluids, this correction has been well-studied by many researchers including Yeh and Hummer (YH); for binary fluid mixtures, a modified YH correction was recently proposed for correcting MD-predicted Maxwell–Stephan (MS) diffusion rates. In this study we use both empirical and machine learning methods to identify improvements to the finite-size correction factors for both self-diffusion and MS diffusion of binary Lennard-Jones (LJ) fluid mixtures. Using artificial neural networks (ANNs), the error in the corrected LJ fluid diffusion is reduced by an order of magnitude versus existing YH corrections, and the ANN models perform well for mixtures with large dissimilarities in size and interaction energies where the YH correction proves insufficient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Revealing the Rate-Limiting Li-Ion Diffusion Pathway in Ultrathick Electrodes for Li-Ion Batteries

Increasing the loading of active materials by thickening the battery electrode coating can enhance the energy density of a Li-ion cell, but the trade-off is the much reduced Li + transport kinetics. To reach the optimum energy and power density for thick electrodes, the effective chemical diffusion coefficient of Li + (D Li ) must be maximized. However, the diffusion of Li + inside an electrode is a complex process involving both microscopic and macroscopic processes. Fundamental understandings are needed on the rate-limiting process that governs the diffusion kinetics of Li + to minimize the negative impact of the large electrode thickness on their electrochemical performance. In this study, lithium Ni–Mn–Co oxide (NMC) cathodes of various thicknesses ranging from 100 to 300 μm were used as a model system to study the rate-limiting diffusion process during charge/discharge. The rate-limiting diffusion coefficient of Li + was investigated and quantified, which was correlated to the electrochemical performance degradation of thick electrodes. Lastly, it is revealed here that the under-utilization of the active material was caused by the limited diffusion of Li + inside the porous electrode, leading to a critical electrode thickness, beyond which the specific capacity was significantly reduced.

25 ENERGY STORAGE↗
DOE OSTI2020

Polymer Conformations and Diffusion Through a Monolayer of Confining Nanoparticles

We present coarse-grained molecular dynamics simulations to probe chain-scale polymer conformations and diffusion between confining nanoparticles (NPs). By constructing a monolayer of hexagonally-packed NPs in a polymer melt with athermal interactions, we observe the magnitude and length-scale over which homogeneously confining NPs impact the polymer behavior, which provides fundamental insights into more complex polymer nanocomposites. We show that polymer conformations are more perturbed under strong confinement (i.e. when the interparticle distance, ID, is less than twice the polymer radius of gyration, 2R g ) as compared to around an isolated NP, and the effect depends on the ratio of R NP /R g rather than either independently. In fact, these conformations can be quantitatively replicated by executing a simple random walk in a similarly confining environment. We also show that polymer diffusion is slowed by the presence of NPs and the slowing persists far beyond the length-scale over which polymer conformations are perturbed. Although the slowing is strongest ~R g from the NPs, the diffusion coefficient is slower even beyond ~5R g from the NPs. Furthermore, by analyzing the directional van Hove distributions, we show polymer diffusion away from the NP monolayer is bulk-like while diffusion through the monolayer is slower with increasing NP confinement. Furthermore, these molecular dynamics simulations provide fundamental insights into the temporal and spatial effect of confining, athermal NPs on chain-scale polymer conformations and diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Increased Polymer Diffusivity in Thin-Film Confinement

In this work, the behavior of polymer melts under planar confinement was investigated using molecular dynamics simulations. Polymers with a range of lengths, from unentangled to highly entangled (N = 25-400), were confined between two discrete-bead parallel walls to create thin films with thicknesses (h = 3.5-40σ, where σ is the unit length) ranging from much larger to much smaller than the polymer size. These simulations were used to measure polymer-chain conformations, entanglement densities, and center-of-mass diffusion, and the results were compared with previous simulations of polymer melts under cylindrical confinement. Changes to the entanglement density and radius of gyration in thin films follow the same behavior as in cylindrical confinement: decreased entanglements per chain, decreased R g perpendicular to the confining wall, and increased R g parallel to the confining wall, though the deviations from bulklike conformations are smaller. Despite similarities in conformation and entanglement behavior between thin-film and cylindrical confinements, the diffusion behavior differs. Under planar confinement, the diffusion coefficient increases monotonically up to 6 times the bulk diffusivity with decreasing film thickness, while it behaves nonmonotonically in cylinders. This is due to the increased degrees of freedom afforded to the polymer chains in a thin film compared to those in a cylinder, allowing chains to diffuse around one another rather than through, as found in cylindrical confinement. Normalized diffusion coefficients, D norm , can be well described by a master curve with an exponential dependence on confinement after scaling D norm by a thickness dependent term.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Li-Ion Diffusion Correlations in LiAlGeO 4 : Quasielastic Neutron Scattering and Ab Initio Simulation

Here, we investigated the impact of Li stoichiometry and host flexibility on Li + diffusion processes in LiAlGeO 4 at the microscopic level using quasielastic neutron scattering (QENS) and ab initio molecular dynamics (AIMD) simulations. Using sufficiently long AIMD trajectories, we could simulate the observed QENS signal and identify the localized dynamics of Li in crystalline LiAlGeO 4 . Such information is vital to identify the bottleneck of diffusion processes and design materials for battery application. Our AIMD simulations in LiAlGeO 4 reveal that the Li + conductivity can be significantly improved by manipulating the Li stoichiometry and/or host flexibility via amorphization. We determined that excess Li stoichiometry enhances the Coulomb repulsion of neighboring Li sites and softens the host structure to enable faster Li + diffusion along the hexagonal c-axis. In the amorphous structure, random orientations of AlO 4 and GeO 4 polyhedral units create a wide distribution of intersite distances and significantly soften the host structure, greatly enhancing the Li + diffusion. The simulations are used to understand the nature of diffusion, especially the role of the host structure, the possible hopping pathways, and the diffusion behavior in various structures of LiAlGeO 4 .

localized dynamics↗
DOE OSTI2022

The Diffusion Mechanism of Ge During Oxidation of Si/SiGe Nanofins

A recently discovered, enhanced Ge diffusion mechanism along the oxidizing interface of Si/SiGe nanostructures has enabled the formation of single-crystal Si nanowires and quantum dots embedded in a defect-free, single-crystal SiGe matrix. Here, we report oxidation studies of Si/SiGe nanofins aimed at gaining a better understanding of this novel diffusion mechanism. Here, a superlattice of alternating Si/Si 0.7 Ge 0.3 layers was grown and patterned into fins. After oxidation of the fins, the rate of Ge diffusion down the Si/SiO 2 interface was measured through the analysis of HAADF-STEM images. The activation energy for the diffusion of Ge down the sidewall was found to be 1.1 eV, which is less than one-quarter of the activation energy previously reported for Ge diffusion in bulk Si. Through a combination of experiments and DFT calculations, we propose that the redistribution of Ge occurs by diffusion along the Si/SiO 2 interface followed by a reintroduction into substitutional positions in the crystalline Si.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Correlating the Viscosity and Rate of Water Diffusion in Semisolid Gel-Forming Aerosol Particles

Aerosol particles are known to exist in highly viscous amorphous states at a low relative humidity and temperature. The slow diffusion of molecules in viscous particles impacts the uptake and loss of volatile and semivolatile species and the rate of heterogeneous chemistry. Recent work has demonstrated that in particles containing organic molecules and salts, the formation of two-phase gel states is possible, leading to observations of rigid particles that resist coalescence. The way that molecules diffuse and transport in gel systems is not well-characterized. In this work, we use an electrodynamic balance to levitate sample particles containing a range of organic compounds in mixtures with calcium chloride and measure the rate of water diffusion. Particles of the pure organics have been shown to form viscous amorphous states, while in mixtures with divalent salts, coalescence measurements have revealed the apparent solidification of particles, consistent with the formation of a gel state facilitated by ion–molecule interactions. We report in several cases that water transport can actually be increased in the rigid gel state relative to the pure compound that forms a viscous state under similar conditions. These measurements reveal the limitations of using viscosity as a metric for predicting molecular diffusion and that the gel structure that forms is a much stronger controlling factor in the rate of diffusion. In conclusion, this underscores the need for diffusion measurements as well as a deeper understanding of noncovalent molecular assembly that leads to supramolecular structures in aerosol particles.

organic-inorganic mixtures↗
DOE OSTI2025

Experimental Characterization of Hydrogen Diffusion in Shale Rocks for Geologic Storage Applications

As global energy systems undergo a transition to cleaner alternatives, geologic hydrogen storage has emerged as a promising solution for large-scale energy storage. A critical factor in determining the feasibility of this approach is the effectiveness of caprock formations, such as shale, in preventing hydrogen migration. This study investigates the diffusion behavior of hydrogen through shale to assess its suitability as a caprock for geologic hydrogen storage. Using a novel double-seal core holder design and a through-diffusion apparatus, hydrogen diffusion was measured through shale rock from the Eagle Ford and Wolfcamp Formations under dry conditions. These measurements were complemented by microstructural and mineralogical analyses using low-pressure nitrogen adsorption and X-ray diffraction. The effective diffusion coefficient of hydrogen in these shale caprocks ranged from 2.51 × 10 –8 to 9.85 × 10 –8 m 2 /s. Notably, we observed that the diffusion behavior was more related to the pore network structure and could not be attributed to differences in the total pore volume between shale types alone. Here, to further understand the role of pore network complexity, a fractal pore model was developed to correlate tortuosity with the fractal dimension of the pore structure (a measure of pore network complexity). The proposed model closely matched tortuosity values obtained from diffusion experiments, outperforming existing theoretical tortuosity–porosity correlations. These findings provide key quantitative parameters needed to assess the feasibility of geologic hydrogen storage as well as insights that can be applied to hydrogen storage in a range of geologic formations.

08 HYDROGEN↗