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At least 469 records · Page 26

Pore connectivity influences mass transport in natural rocks: Pore structure, gas diffusion and batch sorption studies

For this work, six rocks (one granodiorite, one limestone, two chalks, one mudstone, and one dolostone) with different extents of heterogeneity at six different particle sizes (from 75 to 8000 μm) were studied to describe the effects of pore connectivity on mass transport. The methods applied were (i) porosity measurement of granular rocks, (ii) analyses of gas-phase diffusive transport in a bed of packed particles, along with a solid quartz method at these six particle sizes being developed to identify the contribution of intraparticle diffusion, and (iii) batch sorption tests of multiple ions (anions and cations) with subsequent analyses of inductively coupled plasma-mass spectrometry. Granular porosity measurement results reveal that with decreasing particle sizes, the effective porosities for the “heterogenous” group of rocks (Grimsel granodiorite and Edwards limestone) increase, whereas the porosities of another “homogeneous” group (two Israel chalk samples, Japan mudstone, and Wyoming dolostone) remain constant. Gas diffusion results show that the intraparticle gas diffusion coefficient among these two sample groups, varying in the magnitude of 10 -8 to 10 -6 m 2 /s, are not directly correlated to the porosity differences. Moreover, the batch sorption work displays a different affinity of rocks for various tracers. For Grimsel granodiorite, Japan mudstone, and Wyoming dolostone, the adsorption capacity of Sm 3+ and Eu 3+ increases as the particle size decreases. In general, this integrated research of grain size distribution, granular rock porosity, intraparticle diffusivity, and ionic sorption capacity gives insights into the pore connectivity effect on both physical and chemical transport behaviors for different lithologies and/or different particle sizes.

58 GEOSCIENCES↗

Molecular dynamics studies of lattice defect effects on tritium diffusion in zirconium

Tritium diffusion in α-Zr containing point defects such as vacancies or self-interstitial atoms (SIAs) is simulated using molecular dynamics. Point defects rapidly aggregate to form extended defects, such as 3D nanoclusters and Frank loops. The geometry of extended defects is affected by the presence of tritium. At low temperature and in the absence of tritium, vacancies aggregate to form stacking fault pyramids. Addition of tritium at these temperatures promotes aggregation of vacancies to form 3D nanoclusters, within which the tritium concentration can be sufficiently high to suggest that these defects may serve as nucleation sites for hydride precipitation. Trapping of tritium in vacancy nanocluster reduces the calculated bulk diffusivity by an amount proportional to the vacancy concentration. At high temperature, vacancy clusters change shape to form planar basal dislocation loops, which bind tritium less strongly, leading to a sharp reduction in the fraction of trapped tritium and a corresponding increase in tritium diffusivity at high temperature. In contrast, SIAs increase tritium diffusion through α-Zr. Analysis of atomic trajectories shows that tritium does not interact directly with SIAs. In conclusion, diffusion enhancement is instead related to expansion of the lattice.

36 MATERIALS SCIENCE↗

Diffusion and migration in polymer electrolytes

Mixtures of neutral polymers and lithium salts have the potential to serve as electrolytes in next-generation rechargeable Li-ion batteries. The purpose of this review is to expose the delicate interplay between polymer-salt interactions at the segmental level and macroscopic ion transport at the battery level. Since complete characterization of this interplay has only been completed in one system: mixtures of poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI), we focus on data obtained from this system. We begin with a discussion of the activity coefficient, followed by a discussion of six different diffusion coefficients: the Rouse motion of polymer segments is quantified by D seg , the self-diffusion of cations and anions is quantified by D self,+ and D self,- , and the build-up of concentration gradients in electrolytes under an applied potential is quantified by Stefan-Maxwell diffusion coefficients, D 0+ , D 0- , and D +- . The Stefan-Maxwell diffusion coefficients can be used to predict the velocities of the ions at very early times after an electric field is applied across the electrolyte. The surprising result is that D 0- is negative in certain concentration windows. A consequence of this finding is that at these concentrations, both cations and anions are predicted to migrate toward the positive electrode at early times. We describe the controversies that surround this result. Knowledge of the Stefan-Maxwell diffusion coefficients enable prediction of the limiting current. We argue that the limiting current is the most important characteristic of an electrolyte. Excellent agreement between theoretical and experimental limiting current is seen in PEO/LiTFSI mixtures. What sequence of monomers that, when polymerized, will lead to the highest limiting current remains an important unanswered question. It is our hope that the approach presented in this review will guide the development of such polymers.

25 ENERGY STORAGE↗

Microscopic Theory of Long-Time Center-of-Mass Self-Diffusion and Anomalous Transport in Ring Polymer Liquids

We construct a microscopic theory at the level of segment-scale correlated space–time intermolecular forces for the long-time center-of-mass (CM) diffusion constant and intermediate-time non-Fickian transport in dense solutions and melts of ring polymers. The approach combines ideas of polymer, colloid, and liquid-state statistical mechanics to quantify how the multifractal intra-ring conformational structure and inter-ring packing correlations determine dynamic caging constraints and time-dependent friction. Breakdown of Rouse theory is predicted to occur due to length scale-dependent temporal correlation of forces exerted on pairs of tagged ring segments from surrounding polymers. At large enough degrees of polymerization (N), a stronger scaling of the CM diffusion constant (D ∝ N –2 ) is predicted, with a crossover N D proportional to the product of the system-specific macromolecular volume fraction and dimensionless compressibility. In analogy with caging effects in glass-forming fluids, the theory does appear to begin to fail at sufficiently high N/N D for the center-of-mass diffusivity, likely due to another crossover to an even slower activated transport regime. However, use of N/N D with the theoretically predicted N D , in conjunction with dynamic blob scaling ideas for local Rouse friction, collapses semidilute and concentrated solution simulation data onto a master curve. Based on the same physical ideas employed to predict the diffusion constant, a generalized Langevin equation description is formulated for intermediate-time CM transport. It predicts two subdiffusive regimes that emerge due to the self-similar nature of internal ring structure. Analytic and numerical predictions for the apparent non-Fickian exponent as a function of time, N/N D and dimensionless compressibility, the evolution of the maximum degree of subdiffusive motion with N/N D , and the time scale for recovering Fickian diffusion are made, all of which are in good accordance with melt simulations. Furthermore, the present work sets the stage to address activated dynamics and glass formation on the macromolecular scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precise Linker Length and Dynamic Bond Exchange Control Penetrant Diffusion in Dense Vitrimers

Polymer networks with dynamic covalent bonds have been investigated for their self-healing ability, recyclability, and potential as more sustainable materials. Recent results have indicated that in some cases, bond exchange can enhance the transport of penetrants in dense networks, pointing to their potential for separations of membranes. Here, imine dynamic bonds in ethylene oxide (EO) networks with precise linker lengths were synthesized to investigate the transport of N,N′-bis(2,5-di-tert-butylphenyl)-3,4,9,10-perylenedicarboximide (BTBP), a large, anisotropic dye molecule. Networks with mesh sizes smaller than, comparable to, and greater than the size of the penetrant axes were investigated to probe the effects of bond exchange and network confinement on transport. Mesh sizes, which ranged from 0.5 to 1.62 nm, were determined from shear rheology, glass transitions by calorimetry, and probe diffusion coefficients by fluorescence recovery after photobleaching. Permanent networks with identical EO chain lengths were prepared as control samples, and up to a 3 orders of magnitude increase in diffusion coefficient is observed in the dynamic systems for short linkers containing 13 backbone atoms. The longest linkers with 71 backbone atoms show no difference between the permanent and dynamic networks. Linkers shorter than 11 backbone atoms, corresponding to a mesh size smaller than the penetrant small axis, diffusion is no longer observable on the experimental time scale, indicating a sharp cutoff attributed to the precise linkers and narrow mesh size distribution. The dynamic imine exchange time scales were compared to the diffusive hopping times of penetrants and indicate that exchange can occur during a diffusive displacement. Furthermore, these findings provide insights into the factors affecting penetrant transport in dense polymers and inspire the development of next-generation selective polymer membranes.

Diffusion↗

Model for Humidity-Mediated Diffusion on Aluminum Surfaces and Its Role in Accelerating Atmospheric Aluminum Corrosion

Bare aluminum metal surfaces are highly reactive, which leads to the spontaneous formation of a protective oxide surface layer. Because many subsequent corrosive processes are mediated by water, the structure and dynamics of water at the oxide interface are anticipated to influence corrosion kinetics. Here, using molecular dynamics simulations with a reactive force field, we model the behavior of aqueous aluminum metal ions in water adsorbed onto aluminum oxide surfaces across a range of ion concentrations and water film thicknesses corresponding to increasing relative humidity. We find that the structure and diffusivity of both the water and the metal ions depend strongly on the humidity of the environment and the relative height within the adsorbed water film. Aqueous aluminum ion diffusion rates in water films corresponding to a typical indoor relative humidity of 30% are found to be more than 2 orders of magnitude slower than self-diffusion of water in the bulk limit. Connections between metal ion diffusivity and corrosion reaction kinetics are assessed parametrically with a reductionist model based on a 1D continuum reaction–diffusion equation. Our results highlight the importance of incorporating the properties specific to interfacial water in predictive models of aluminum corrosion.

36 MATERIALS SCIENCE↗

Influence of Rigidity–Hydration Coupling on Size-Dependent Diffusion in Hydrated Polymer Membranes

Selective ion transport in polymer membranes depends critically on how penetrant motion couples to polymer dynamics and hydration. Yet, the mechanistic interplay between polymer rigidity, water content, and penetrant size remains poorly understood, especially in the regime where the penetrant diameter, polymer Kuhn length, and correlation length are comparable. Here, we employ coarse-grained molecular dynamics simulations to systematically investigate penetrant diffusion in hydrated polymer networks across a broad range of water volume fractions, chain rigidities, and penetrant sizes. The results reveal a transition from a decoupled regime, where small penetrants diffuse nearly independently of polymer relaxation, to a coupled regime in which large penetrants require cooperative polymer motion for transport. Increasing polymer rigidity amplifies the sensitivity of diffusivity to hydration, particularly at low water content, leading to pronounced deviations from Stokes−Einstein scaling. Comparison with scaling theories and free-volume models shows that classical nanoparticle-based frameworks fail to capture this intermediate regime. To address this gap, we extend the Yasuda model to incorporate polymer rigidity through a single parameter that quantifies the dynamic contribution of chain stiffness to free-volume fluctuations. The resulting model collapses diffusivity data across all sizes, water contents, and rigidities, providing a unified description of penetrant transport in hydrated polymer matrices. Furthermore, these findings establish polymer rigidity as a key, tunable determinant of diffusion and offer a framework for interpreting size-dependent transport in ion-selective membranes.

diffusion↗

Surface Self-Diffusion Induced Sintering of Nanoparticles

Despite the critical role of sintering phenomena in constraining the long-term durability of nanosized particles, a clear understanding of nanoparticle sintering has remained elusive due to the challenges in atomically tracking the neck initiation and discerning different mechanisms. Through the integration of in situ transmission electron microscopy and atomistic modeling, this study uncovers the atomic dynamics governing the neck initiation of Pt–Fe nanoparticles via a surface self-diffusion process, allowing for coalescence without significant particle movement. Real-time imaging reveals that thermally activated surface morphology changes in individual nanoparticles induce significant surface self-diffusion. Further, the kinetic entrapment of self-diffusing atoms in the gaps between closely spaced nanoparticles leads to the nucleation and growth of atomic layers for neck formation. This surface self-diffusion-driven sintering process is activated at a relatively lower temperature compared to the classic Ostwald ripening and particle migration and coalescence processes. The fundamental insights have practical implications for manipulating the morphology, size distribution, and stability of nanostructures by leveraging surface self-diffusion processes.

36 MATERIALS SCIENCE↗

Charge Carrier and Spin Diffusion in a Polycrystalline and Single Crystal Lead Halide Perovskite Semiconductor

The directed movement of spin-bearing excitations in semiconductors can enable many potential schemes for spintronic applications. Understanding the mechanism of spin motion, as opposed to charge carrier or exciton motion, may require specialized techniques and sample conditions. Here we employ the noncontact and time-resolved technique of light-induced transient grating spectroscopy (LITG) to measure both carrier and spin motion in a perovskite semiconductor with varying crystallinity. The carrier motion aligns with expectations from past studies undertaken at low fluence, revealing an ambipolar diffusion coefficient on the order of 1 cm 2 /sec and diffusion length of roughly 1.5 μm for single crystals that is strongly attenuated as crystallite size decreases. The spin diffusion is measured with cross-polarized excitation beams and uncovers an intensity-dependent coefficient rising above 100 cm 2 /sec. The fast room-temperature spin relaxation limits the spin diffusion length, but the remarkable speedup of spin over carrier diffusion suggests a mechanism involving a combination of exchange-mediated and doping effects that enhance spin transport.

14 SOLAR ENERGY↗

Superionic-like diffusion in yttrium dihydride

For the next-generation high temperature microreactors, yttrium dihydride (YH 2 ) is an attractive solid state neutron moderator. Despite a number of recent investigations, the mechanism of hydrogen transport remains poorly understood. Experimental evaluations of diffusivity are inconclusive with large variations in diffusivities and activation energies. In this work, we perform ab initio molecular dynamics (AIMD) simulations on YH 2 for temperatures spanning 300 K to 1200 K. Our main finding is that YH 2 shows a superionic-like behavior with hydrogen atoms hopping from one native site to another above a characteristic temperature of 800 K. This correlated motion results in quasi-one-dimensional string-like displacements that enable the hydrogen atoms to diffuse rapidly. We confirm that the octahedral sites are mostly unoccupied, although channeling through them is the most favored pathway between lattice hops above 800 K. At the highest temperature of 1200 K, the string relaxation time is merely of the order of a few picoseconds, which indicates a liquid-like diffusive behavior. Based on the formation of spontaneous thermal vacancies, an order-disorder crossover temperature T α ~ 800 K is established for YH 2 with an activation energy of 0.83 eV for hydrogen diffusion in the superionic-like state.

Superionic-like Diffusion↗

Effect of diffusion constant on the morphology of dendrite growth in lithium metal batteries

Lithium dendrites can lead to a short circuit and battery failure, and developing strategies for their suppression is of considerable importance. In this work, we study the growth of dendrites in a simple model system where the solvent is a continuum and the lithium ions are hard spheres that can deposit by sticking to existing spheres or the electrode surface. Using stochastic dynamics simulations, we investigate the effect of applied voltage and diffusion constant on the growth of dendrites. We find that the diffusion constant is the most significant factor, and the inhomogeneity of the electric field does not play a significant role. Additionally, the growth is most pronounced when the applied voltage and diffusion constant are both low. We observe a structural change from broccoli to cauliflower shape as the diffusion constant is increased. The simulations suggest that a control of electrolyte parameters that impact lithium diffusion might be an attractive route to controlling dendrite growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-consistent hopping theory of activated relaxation and diffusion of dilute penetrants in dense crosslinked polymer networks

We generalize a microscopic statistical mechanical theory of the activated dynamics of dilute spherical penetrants in glass-forming liquids to study the influence of crosslinking in polymer networks on the penetrant relaxation time and diffusivity over a wide range of temperature and crosslink fraction (f n ). Our calculations are relevant to recent experimental studies of a nm-sized molecule diffusing in poly-(n-butyl methacrylate) networks. The theory predicts the penetrant relaxation time increases exponentially with the glass transition temperature, T g (f n ), which grows roughly linearly with the square root of fn due to the coupling of local hopping to longer-range collective elasticity. Moreover, T g is also found to be proportional to a geometric confinement parameter defined as the ratio of the penetrant diameter to the mean network mesh size. The decoupling ratio of the penetrant and Kuhn segment alpha times displays a complex non-monotonic dependence on f n and temperature that is well collapsed based on the variable T g (f n )/T. A model for the penetrant diffusion constant that combines activated relaxation and entropic mesh confinement is proposed, which results in a significantly stronger suppression of mass transport with degree of effective supercooling than predicted for the penetrant alpha time. Furthermore, this behavior corresponds to a new network-based type of “decoupling” of diffusion and relaxation. In contrast to the diffusion of larger nanoparticles in high temperature rubbery networks, our analysis in the supercooled regime suggests that for the penetrants studied the mesh confinement effects are of secondary importance relative to the consequences of crosslink-induced slowing down of activated hopping of glassy physics origin.

Chemistry↗

Minimizing the diffusivity difference between vacancies and interstitials in multi-principal element alloys

Interstitial atoms usually diffuse much faster than vacancies, which is often the root cause for the ineffective recombination of point defects in metals under irradiation. Here, via ab initio modeling of single-defect diffusion behavior in the equiatomic NiCoCrFe(Pd) alloy, we demonstrate an alloy design strategy that can reduce the diffusivity difference between the two types of point defects. The two diffusivities become almost equal after substituting the NiCoCrFe base alloy with Pd. The underlying mechanism is that Pd, with a much larger atomic size (hence larger compressibility) than the rest of the constituents, not only heightens the activation energy barrier ( E a ) for interstitial motion by narrowing the diffusion channels but simultaneously also reduces E a for vacancies due to less energy penalty required for bond length change between the initial and the saddle states. Our findings have a broad implication that the dynamics of point defects can be manipulated by taking advantage of the atomic size disparity, to facilitate point-defect annihilation that suppresses void formation and swelling, thereby improving radiation tolerance.

36 MATERIALS SCIENCE↗

Odd Diffusivity of Chiral Random Motion

Diffusive transport is characterized by a diffusivity tensor which may, in general, contain both a symmetric and an antisymmetric component. Although the latter is often neglected, we derive Green-Kubo relations showing it to be a general characteristic of random motion breaking time-reversal and parity symmetries, as encountered in chiral active matter. In analogy with the odd viscosity appearing in chiral active fluids, we term this component the odd diffusivity. Furthermore, we show how odd diffusivity emerges in a chiral random walk model, and demonstrate the applicability of the Green-Kubo relations through molecular dynamics simulations of a passive tracer particle diffusing in a chiral active bath.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of transport mechanism on the coarsening of bicontinuous structures: A comparison between bulk and surface diffusion

Here, coarsening of bicontinuous microstructures is observed in a variety of systems, such as nanoporous metals and mixtures that have undergone spinodal decomposition. To better understand the morphological evolution of these structures during coarsening, we compare the morphologies resulting from two different coarsening mechanisms, surface and bulk diffusion. We perform phase-field simulations of coarsening via each mechanism in a two-phase mixture at nominal volume fractions of 50%-50% and 36%-64%, and the simulated structures are characterized in terms of topology (genus density), the interfacial shape distribution, structure factor, and autocorrelations of phase and mean curvature. We observe self-similar evolution of morphology and topology and agreement with the expected power laws for dynamic scaling, in which the characteristic length scale increases over time proportionally to t 1/4 for surface diffusion and t 1/3 for bulk diffusion. While we observe the expected difference in the coarsening kinetics, we find that differences in self-similar morphology due to coarsening mechanism are relatively small, although typically they are larger at 36% volume fraction than at 50% volume fraction. In particular, we find that bicontinuous structures coarsened via surface diffusion have lower scaled genus densities than structures coarsened via bulk diffusion. We also compare the self-similar morphologies to those in literature and to two model bicontinuous structures, namely, constant-mean-curvature surfaces based on the Schoen G minimal surface and random leveled-wave structures. The average scaled mean curvatures of these model structures agree reasonably with those of the coarsened structures at both 36% and 50%, but we find substantial disagreements in the scaled genus densities and the standard deviations of mean curvature.

36 MATERIALS SCIENCE↗

Asymptotically Compatible Reproducing Kernel Collocation and Meshfree Integration for Nonlocal Diffusion

Reproducing kernel (RK) approximations are meshfree methods that construct shape functions from sets of scattered data. We present an asymptotically compatible (AC) RK collocation method for nonlocal diffusion models with Dirichlet boundary condition. The numerical scheme is shown to be convergent to both nonlocal diffusion and its corresponding local limit as nonlocal interaction vanishes. The analysis is carried out on a special family of rectilinear Cartesian grids for a linear RK method with designed kernel support. The key idea for the stability of the RK collocation scheme is to compare the collocation scheme with the standard Galerkin scheme, which is stable. In addition, assembling the stiffness matrix of the nonlocal problem requires costly computational resources because high-order Gaussian quadrature is necessary to evaluate the integral. We thus provide a remedy to the problem by introducing a quasi-discrete nonlocal diffusion operator for which no numerical quadrature is further needed after applying the RK collocation scheme. The quasi-discrete nonlocal diffusion operator combined with RK collocation is shown to be convergent to the correct local diffusion problem by taking the limits of nonlocal interaction and spatial resolution simultaneously. The theoretical results are then validated with numerical experiments. We additionally illustrate a connection between the proposed technique and an existing optimization based approach based on generalized moving least squares.

97 MATHEMATICS AND COMPUTING↗

A Probabilistic Scheme for Semilinear Nonlocal Diffusion Equations with Volume Constraints

This work presents a probabilistic scheme for solving semilinear nonlocal diffusion equations with volume constraints and integrable kernels. The nonlocal model of interest is defined by a time-dependent semilinear partial integro-differential equation (PIDE), in which the integro-differential operator consists of both local convection-diffusion and nonlocal diffusion operators. Here, our numerical scheme is based on the direct approximation of the nonlinear Feynman–Kac formula that establishes a link between nonlinear PIDEs and stochastic differential equations. The exploitation of the Feynman–Kac representation avoids solving dense linear systems arising from nonlocal operators. Compared with existing stochastic approaches, our method can achieve first-order convergence after balancing the temporal and spatial discretization errors, which is a significant improvement of existing probabilistic/stochastic methods for nonlocal diffusion problems. Error analysis of our numerical scheme is established. The effectiveness of our approach is shown in two numerical examples. The first example considers a three-dimensional nonlocal diffusion equation to numerically verify the error analysis results. The second example presents a physics problem motivated by the study of heat transport in magnetically confined fusion plasmas.

97 MATHEMATICS AND COMPUTING↗

Transmural Remodeling of Cardiac Microstructure in Aged Spontaneously Hypertensive Rats by Diffusion Tensor MRI

The long-standing high blood pressure (also known as hypertension) overworks the heart. Microstructural remodeling is a key factor of hypertensive heart disease progression. Diffusion tensor magnetic resonance imaging (DT-MRI) is a powerful tool for the rapid noninvasive nondestructive delineation of the cardiomyocyte organization. The spontaneously hypertensive rat (SHR) is a well-established model of genetic hypertension. The goal of this study was to employ high-resolution DT-MRI and the SHR animal model to assess the transmural layer-specific remodeling of myocardial microstructure associated with hypertension. Ex vivo experiments were performed on excised formalin-fixed hearts of aged SHRs (n = 4) and age-matched controls (n = 4). The DT-MRI-derived fractional anisotropy (FA), longitudinal diffusivity (λ L ), transversal diffusivity (λ T ), and mean diffusivity (MD) served as the readout parameters investigated at three transmural zones (i.e., endocardium, mesocardium, and epicardium). The helix angles (HAs) of the aggregated cardiomyocytes and the orientation of laminar sheetlets were also studied. Compared with controls, the SHRs exhibited decreased epicardial FA, while FA changes in the other two transmural regions were insignificant. No substantial differences were observed in the diffusivity parameters and the transmural course of HAs between the two groups. A consistent distribution pattern of laminar sheetlet orientation was not identified for either group. Our findings are in line with the known cellular microstructure from early painstaking histological studies. Biophysical explanations of the study outcomes are provided. In conclusion, our experimental findings indicate that the epicardial microstructure is more vulnerable to high blood pressure leading to more pronounced changes in this region during remodeling. DT-MRI is well-suited for elucidating these alterations. The revealed transmural nonuniformity of myocardial reorganization may shed light on the mechanisms of the microstructure-function relationship in hypertension progression. Our results provide insights into the management of patients with systemic arterial hypertension, thus prevent the progression toward heart failure. The findings of this study should be acknowledged by electromechanical models of the heart that simulate the specific cardiac pathology.

60 APPLIED LIFE SCIENCES↗