Search NASA⌕ Search

SEARCH · Search NASA

Results for “Percolation”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Composite-Based High Performance Electroactive Polymers For Remotely Controlled Mechanical Manipulations in NASA Applications

This program supported investigation of an all-polymer percolative composite which exhibits very high dielectric constant (less than 7,000). The experimental results show that the dielectric behavior of this new class of percolative composites follows the prediction of the percolation theory and the analysis of the conductive percolation phenomena. The very high dielectric constant of the all-polymer composites which are also very flexible and possess elastic modulus not very much different from that of the insulation polymer matrix makes it possible to induce a high electromechanical response under a much reduced electric field (a strain of 2.65% with an elastic energy density of 0.18 J/cu cm can be achieved under a field of 16 MV/m). Data analysis also suggests that in these composites, the non-uniform local field distribution as well as interface effects can significantly enhance the strain responses. Furthermore, the experimental data as well as the data analysis indicate that the conduction loss in these composites will not affect the strain hysteresis.

Zhang, Q. M.↗
NASA NTRS2022

An Empirical Algorithm to Map Perennial Firn Aquifers and Ice Slabs Within the Greenland Ice Sheet Using Satellite L-band Microwave Radiometry

Perennial firn aquifers are subsurface meltwater reservoirs consisting of a meters-thick water-saturated firn layer that can form on spatial scales as large as tens of kilometers. They have been observed within the percolation facies of glaciated regions experiencing intense seasonal surface melting and high snow accumulation. Widespread perennial firn aquifers have been identified within the Greenland Ice Sheet (GrIS) via field expeditions, airborne ice-penetrating radar surveys, and satellite microwave sensors. In contrast, ice slabs are nearly continuous ice layers that can also form on spatial scales as large as tens of kilometers as a result of surface and subsurface water-saturated snow and firn layers sequentially refreezing following multiple melting seasons. They have been observed within the percolation facies of glaciated regions experiencing intense seasonal surface melting but in areas where snow accumulation is at least 25 % lower as compared to perennial firn aquifer areas. Widespread ice slabs have recently been identified within the GrIS via field expeditions and airborne ice-penetrating radar surveys, specifically in areas where perennial firn aquifers typically do not form. However, ice slabs have yet to be identified from space. Together, these two ice sheet features represent distinct, but related, sub-facies within the broader percolation facies of the GrIS that can be defined primarily by differences in snow accumulation, which influences the englacial hydrology and thermal characteristics of firn layers at depth. Here, for the first time, we use enhanced-resolution vertically polarized L-band brightness temperature () imagery (2015–2019) generated using observations collected over the GrIS by NASA's Soil Moisture Active Passive (SMAP) satellite to map perennial firn aquifer and ice slab areas together as a continuous englacial hydrological system. We use an empirical algorithm previously developed to map the extent of Greenland's perennial firn aquifers via fitting exponentially decreasing temporal L-band signatures to a set of sigmoidal curves. This algorithm is recalibrated to also map the extent of ice slab areas using airborne ice-penetrating radar surveys collected by NASA's Operation IceBridge (OIB) campaigns (2010–2017). Our SMAP-derived maps show that between 2015 and 2019, perennial firn aquifer areas extended over 64 000 km2, and ice slab areas extended over 76 000 km2. Combined together, these sub-facies are the equivalent of 24 % of the percolation facies of the GrIS. As Greenland's climate continues to warm, seasonal surface melting will increase in extent, intensity, and duration. Quantifying the possible rapid expansion of these sub-facies using satellite L-band microwave radiometry has significant implications for understanding ice-sheet-wide variability in englacial hydrology that may drive meltwater-induced hydrofracturing and accelerated ice flow as well as high-elevation meltwater runoff that can impact the mass balance and stability of the GrIS.

Julie Z Miller↗
DOE OSTI2026

Heterogeneous Corrosion Pathways in Pt–Ni Nanododecahedra Revealed by In Situ Liquid Cell TEM

Unraveling nanoscale corrosion pathways is essential for understanding materials degradation mechanisms and designing corrosion-resistant metal alloys. Here, in this study, we directly visualize the corrosion of Pt–Ni nanododecahedra in 0.1 M HCl using liquid cell TEM. Each nanoparticle features a Ni-rich core and a Pt-rich frame. Our observation reveals that corrosion proceeds in two distinct stages: first the Ni-rich core dissolves without forming porosity, yielding small Pt nanocrystals and transient NiCl 2 ·6H 2 O at the retreating interfaces; then the Pt-rich frame fragments into ∼5 nm Pt 3 Ni nanocrystals that subsequently dissolve uniformly, accompanied by fleeting Pt chlorides. A percolation-based theory explains the observed behaviors: The core’s ∼8% Pt lies below the Pt connectivity threshold, preventing Pt scaffold formation, whereas the frame’s 48% Ni exceeds the Ni percolation threshold and collapses. Ordered Pt 3 Ni suppresses Ni percolation, thereby enforcing uniform dissolution. These findings reveal how composition and structural ordering govern heterogeneous corrosion in Pt–Ni architectured nanoparticles.

Liquid phase TEM↗
DOE OSTI2022

Distribution Cutoff for Clusters near the Gel Point

The mechanical and dynamic properties of developing networks near the gel point are susceptible to the distribution of clusters coexisting with percolating networks. The distribution of cluster numbers follows a broad power law, wrapped by a cutoff function that rapidly decays at a characteristic size. The form of the cutoff function has been speculated based on known results from lattice percolation and, in certain cases, solved. We obtained this cutoff function from simulated dynamic clusters of polymeric precursor chains using a hybrid Monte Carlo algorithm. The results obtained from three different precursor chain lengths are consistent with each other and are consistent with the expectation from lattice percolation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

2016 Waste Management Monitoring Report Area 3 and Area 5 Radioactive Waste Management Sites

Environmental monitoring data are collected at and around the Area 3 and Area 5 Radioactive Waste Management Sites (RWMSs) within the Nevada National Security Site (NNSS). These data include direct radiation exposure, as well as radiation from the air, groundwater, meteorology, and vadose zone. This report summarizes the 2016 environmental data to provide an overall evaluation of RWMS performance and to support environmental compliance and performance assessment (PA) activities. Some of these data (e.g., radiation exposure, air, and groundwater) are presented in other reports, developed by National Security Technologies, LLC Direct radiation monitoring data indicate exposure levels at the RWMSs are within the range of background levels measured at the NNSS. Slightly elevated exposure levels outside the Area 3 RWMS are attributed to nearby historical aboveground nuclear weapons tests. Air monitoring data show that tritium concentrations in water vapor and americium and plutonium concentrations in air particles are below Derived Concentration Standards for these radionuclides. Groundwater monitoring data indicate the groundwater in the uppermost aquifer beneath the Area 5 RWMS is not impacted by RWMS operations. Results of groundwater analysis from wells around the Area 5 RWMS were all below established investigation levels. Leachate samples collected from the leachate collection system at the mixed low-level waste cell were below established contaminant regulatory limits. During 2016, precipitation at the Area 3 RWMS was 8% below average, and precipitation at the Area 5 RWMS was 8% above average. Water balance measurements indicate that evapotranspiration from the vegetated weighing lysimeter dries the soil and prevents downward percolation of precipitation more effectively than evaporation as measured from the bare-soil weighing lysimeter. Vadose zone monitoring on Area 5 and Area 3 RWMS cell covers shows no evidence of precipitation percolating through the covers to the waste. Moisture from precipitation did not percolate below 150 centimeters (cm) (5 feet [ft]) in the vegetated final cover on the U-3ax/bl disposal unit at the Area 3 RWMS. During 2016, there was no drainage through 2.4 meters (8 ft) of soil as indicated from the Area 3 drainage lysimeters that received only natural precipitation. Forty-four percent of the applied precipitation and irrigation drained from the bare-soil drainage lysimeter, which received 3 times the natural precipitation. All 2016 monitoring data indicate that the Area 3 and Area 5 RWMSs are performing within expectations of the model and parameter assumptions for the facilities’ PAs

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Nevada National Security Site 2015 Waste Management Monitoring Report Area 3 and Area 5 Radioactive Waste Management Sites

Environmental monitoring data are collected at and around the Area 3 and Area 5 Radioactive Waste Management Sites (RWMSs) within the Nevada National Security Site (NNSS). These data include direct radiation exposure, as well as radiation from the air, groundwater, meteorology, and vadose zone. This report summarizes the 2015 environmental data to provide an overall evaluation of RWMS performance and to support environmental compliance and performance assessment (PA) activities. Some of these data (e.g., radiation exposure, air, and groundwater) are presented in other reports developed by National Security Technologies, LLC. Direct radiation monitoring data indicate exposure levels at the RWMSs are within the range of background levels measured at the NNSS. Slightly elevated exposure levels outside the Area 3 RWMS are attributed to nearby historical aboveground nuclear weapons tests. Air monitoring data show that tritium concentrations in water vapor and americium and plutonium concentrations in air particles are below Derived Concentration Standards for these radionuclides. Groundwater monitoring data indicate the groundwater in the uppermost aquifer beneath the Area 5 RWMS is not impacted by RWMS operations. Results of groundwater analysis from wells around the Area 5 RWMS were all below established investigation levels. Leachate samples collected from the leachate collection system at the mixed low-level waste cell were below established contaminant regulatory limits. During 2015, precipitation at the Area 3 RWMS was 0.9% above average, and precipitation at the Area 5 RWMS was 25% above average. Water balance measurements indicate that evapotranspiration from the vegetated weighing lysimeter dries the soil and prevents downward percolation of precipitation more effectively than evaporation as measured from the bare-soil weighing lysimeter. The 1.8 inches of precipitation in September reached the lowest sensors at 180 cm on the Cell 5S and 5N covers, however the sensors on the floor do not indicate any signs of the precipitation percolating thru the waste to the floor. Moisture from precipitation did not percolate below 150 centimeters (cm) (5 feet [ft]) in the vegetated final cover on the U-3ax/bl disposal unit at the Area 3 RWMS. A second remedial revegetation trial was done on the southern portion of the North Cover. In March 2015 it was determined that germination occurred on both the mulched and non-mulched treatments that were irrigated, but that no germination occurred on the non-irrigated treatments. By June the seedlings observed in March were gone, possibly grazed by rabbits which were observed inside the rabbit-proof fence. In August the entire area was sprayed with the herbicide glyphosate in an attempt to minimize weed seed production. During 2015, there was no drainage through 2.4 meters (8 ft) of soil as indicated from the Area 3 drainage lysimeters that received only natural precipitation. Thirty-one percent of the applied precipitation and irrigation drained from the bare-soil drainage lysimeter, which received 3 times the natural precipitation. All 2015 monitoring data indicate that the Area 3 and Area 5 RWMSs are performing within expectations of the model and parameter assumptions for the facilities’ PAs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Rational Strategy to Stabilize an Unstable High‐Efficiency Binary Nonfullerene Organic Solar Cells with a Third Component

Abstract Long device lifetime is still a missing key requirement in the commercialization of nonfullerene acceptor (NFA) organic solar cell technology. Understanding thermodynamic factors driving morphology degradation or stabilization is correspondingly lacking. In this report, thermodynamics is combined with morphology to elucidate the instability of highly efficient PTB7‐Th:IEICO‐4F binary solar cells and to rationally use PC 71 BM in ternary solar cells to reduce the loss in the power conversion efficiency from ≈35% to <10% after storage for 90 days and at the same time improve performance. The hypomiscibility observed for IEICO‐4F in PTB7‐Th (below the percolation threshold) leads to overpurification of the mixed domains. By contrast, the hypermiscibility of PC 71 BM in PTB7‐Th of 48 vol% is well above the percolation threshold. At the same time, PC 71 BM is partly miscible in IEICO‐4F suppressing crystallization of IEICO‐4F. This work systematically illustrates the origin of the intrinsic degradation of PTB7‐Th:IEICO‐4F binary solar cells, demonstrates the structure–function relations among thermodynamics, morphology, and photovoltaic performance, and finally carries out a rational strategy to suppress the degradation: the third component needs to have a miscibility in the donor polymer at or above the percolation threshold, yet also needs to be partly miscible with the crystallizable acceptor.

Zhu, Youqin↗
DOE OSTI2020

Dynamic domain kinematic modelling for predicting interflow over leaky impeding layers

Traditional Boussinesq or kinematic simulations of interflow (i.e., lateral subsurface flow) assume no leakage through the impeding layer and require a no-flow boundary condition at the ridge top. However, recent analyses of many interflow-producing landscapes indicate that leaky impeding layers are common, that most interflow percolates well before reaching the toe slope, and therefore, the downslope contributing length is shorter than the hillslope length. In watersheds characterised by perched interflow over a low conductivity layer through permeable topsoil, interflow with percolation may be modelled with a kinematic wave model using a mobile upslope boundary condition defining the hillslope portion contributing interflow to valleys. Here, we developed and applied a dynamic interflow model to simulate interflow using a downslope travel distance concept such that only the active contributing length is modelled at any time. The model defines a variable active area based on the depth of the perched layer, the topographic slope and the ratio of the hydraulic conductivity of topsoil to that of the impeding layer. It incorporates a two-layer soil moisture accounting water balance analysis, a pedo-transfer function, and percolation and evaporation routines to predict interflow rates in continuous and event-based scenarios. We tested the modelling concept on two sets of data (2-year dataset of rainfall observations for the continuous simulation and a multi-day irrigation experiment for the event simulation) from a 121-m-long open interflow collection trench on an experimental hillslope at the Savannah River Site, South Carolina. The continuous model simulation partially represented the observed interflow hydrograph and perched water depth in the experimental hillslope with correlation coefficients of 0.85 and 0.35, respectively. Model performance improved significantly at event-scale analysis. The modelling approach realistically represents interflow dynamics in hillslopes with leaky impeding layers and can be integrated into catchment-scale hydrology models for more detailed hillslope process modelling.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Effect of spatial distribution of polymer fibers on preventing spalling of UHPC at high temperatures

Polypropylene (PP) fibers are commonly used for the prevention of thermal spalling of ultra-high performance concrete (UHPC). In this work, the effect of fiber distribution on permeability and spalling resistance is investigated and an analytical model for permeability at 150 °C is proposed. This model, considering the parameters like fiber dimensions, dosage, and percolation, is based on Kozeny-Carman equation. It was found that the percolation of the interconnecting fiber network resulted in a significant increase in permeability of UHPC. X-ray tomography data on the three-dimensional spatial distribution of fibers reiterated that fiber aspect ratio and dosage (and fiber number density) were critical in increasing the fiber connectivity (percolation). It was also found that a vapor permeability of larger than 0.6 × 10{sup −16} m{sup 2} at 150 °C could eliminate spalling. Further, based on a semi-empirical approach, aspect ratio between 300 and 600 was recommended for spalling prevention with a fiber dosage of 0.3–0.4 vol%.

36 MATERIALS SCIENCE↗
DOE OSTI2018

On the existence and origin of sluggish diffusion in chemically disordered concentrated alloys

Concentrated single phase solid solutions, including medium- and high-entropy alloys, represent a new class of materials that have recently attracted significant interest due to exceptional functional and structural properties. Their fascinating properties are mainly attributed to the sluggish atomic-level diffusion and transport, but its controlling mechanisms are largely unknown and there is certain skepticism about its very existence. By using microsecond-scale molecular dynamics, on-the-fly and conventional kinetic Monte Carlo, we reveal the governing role of percolation effects and composition dependence of the vacancy migration energy in diffusion. Surprisingly, an increase of concentration of faster species (Fe) in face-centered cubic Ni-Fe alloy may decrease the overall atomic diffusion. Consequently, the composition dependence of tracer diffusion coefficient has a minimum near the site percolation threshold, ~20 at.%Fe. We argue that this coupled percolation and composition-dependent barriers for vacancy jumps within different subsystems in medium- and high-entropy alloys leads, indeed, to the sluggish diffusion. A fast method for preselecting materials with potentially desired properties is suggested.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Generation and healing of porosity in high purity copper by high-pressure torsion

Highlights: • Direct characterization of severe plastic deformation induced and healed porosities. • HPT process of disk with pre-fabricated holes reveals healing of porosity. • Ultrafine grains coexisting with shear bands and pores exhibit high stability. • Excess vacancies and pores cause drag effect on the grain boundary motion. • Accelerated vacancy diffusion leads to the generation and growth of pores. - Abstract: Generation and healing of pores in metals under loading or during processing have long been important research topics, and their mechanisms are still debatable. In recent years, unexpected percolating networks of pores acting as ultra-fast diffusion paths were found in ultrafine-grained metals processed by severe plastic deformation. Herein, we conducted a systematic study of the mechanisms of generation and healing of pores in ultrahigh-purity copper (99.9995 wt%) during high-pressure torsion (HPT). In addition to a solid Cu disk, the disk with holes that were drilled before processing, resulting in nominal initial porosity of 4.48%, was processed by HPT. After HPT, the percolating porosities of 0.07 ± 0.01% and 0.04 ± 0.01% were found in the solid disk, and in the disk with pre-fabricated holes, respectively. Thus, higher initial porosity resulted in lower percolating porosity in the HPT-processed disk. Systemic characterization using scanning electron microscopy revealed that in both cases shear bands and ultra-fine grains are located in the regions with induced and healed pores. We discussed the mechanisms of porosity evolution in both cases. In the end, to verify the possibility of pores nucleation and growth by vacancy agglomeration, vacancy diffusivity during HPT processing was estimated. This work sheds a new light on the mechanisms of pores nucleation and evolution during severe plastic deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Non-equilibrium simulations of hydraulic permeation: Role of mechanical boundary conditions in dense membranes

Understanding the mechanisms of water transport in reverse osmosis membranes is critical for improving membrane performance and guiding material design. While classical models describe transport as either solution-diffusion (SD)—involving concentration-driven diffusion through a homogeneous medium—or pore-flow (PF)—involving pressure-driven convection through percolated water channels—their applicability to crosslinked polyamide membranes remains debated. Here, using non-equilibrium molecular dynamics simulations, we investigate the impact of mechanical support conditions on pressure-driven water transport in polyamide membranes across varying crosslink densities and pressure differentials (1000–5000 bar). Two support conditions are considered: graphene-restrained, representing experimentally relevant supported membranes, and freeze-restrained, mimicking a self-supported structure. In graphene-restrained systems, water concentration gradients and constant pressure profiles emerge, consistent with SD theory and incompatible with PF assumptions due to the absence of percolated pores and sub-nanometer voids. In contrast, freeze-restrained systems display uniform water concentration and linearly decreasing pressure at 1000 bar, and exhibit compressibility-induced water gradients and partial percolation at 5000 bar, resembling PF-like behavior. However, the underlying assumptions of PF theory—continuous solvent pathways and pressure transmission through water-filled pores—are not met under most conditions. Our results demonstrate that accurate modeling of reverse osmosis membranes must incorporate realistic mechanical boundary conditions to distinguish between transport mechanisms. For dense polyamide membranes supported by porous substrates, graphene-restrained simulations best reflect experimental setups and support the SD model as the dominant mechanism of water permeation.

molecular dynamics↗
DOE OSTI2026

Correlated Ion Transport Governed by Dynamic Local Structure in High Concentration and Localized High Concentration Electrolytes

Understanding the dynamics of cluster formation and network percolation provides the mechanistic link between microscopic solvation structure and transport in concentrated electrolytes, including localized high-concentration electrolytes (LHCEs). Although recent studies have shown LHCEs to form micelle-like aggregates at specific compositions, a quantitative understanding of how solvation structures and transport properties depend on salt–solvent–diluent ratios remains limited. Here, we integrate molecular dynamics with Onsager transport analyses to chart the evolution of solvation microstructure and associated ionic transport in LiFSI/DMC/TTE, achieving good agreement with experimental conductivities across composition. We show that micelle formation arises from a dynamic instability of the cation–anion network, and that network percolation is the primary determinant of conductivity. Two compositional thresholds emerge: A critical network concentration (CNC) and a critical micelle concentration (CMC) that delineate transitions from extended percolating networks to micelle-like clusters and then to fragments. These structural transitions rationalize the nonintuitive conductivity decrease at intermediate dilution despite monotonically decreasing viscosity and provide composition-level design rules for LHCEs.

Mohanakrishnan, Rohith Srinivaas [University of Ca↗
DOE OSTI2015

Aggregation of heteropolyanions in aqueous solutions exhibiting short-range attractions and long-range repulsions

Charged colloids and proteins in aqueous solutions interact via short-range attractions and long-range repulsions (SALR) and exhibit complex structural phases. These include homogeneously dispersed monomers, percolated monomers, clusters, and percolated clusters. We report the structural architectures of simple charged systems in the form of spherical, Keggin-type heteropolyanions (HPAs) by small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations. Structure factors obtained from the SAXS measurements show that the HPAs interact via SALR. Concentration and temperature dependences of the structure factors for HPAs with –3e (e is the charge of an electron) charge are consistent with a mixture of nonassociated monomers and associated randomly percolated monomers, whereas those for HPAs with –4e and –5e charges exhibit only nonassociated monomers in aqueous solutions. Our experiments show that the increase in magnitude of the charge of the HPAs increases their repulsive interactions and inhibits their aggregation in aqueous solutions. MD simulations were done to reveal the atomistic scale origins of SALR between HPAs. As a result, the short-range attractions result from water or proton-mediated hydrogen bonds between neighboring HPAs, whereas the long-range repulsions are due to the distributions of ions surrounding the HPAs.

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

Impact of an Emergent Hierarchical Filler Network on Nanocomposite Dynamics

Aggregated polymer fillers, such as carbon black and silica, at concentrations above the percolation threshold form an emergent structure, the hierarchical filler network, in immiscible systems where dispersion is driven by accumulated strain. It is proposed that the hierarchical filler network is composed of a primary nanoscale network that locally percolates at ~5 vol % of aggregates, associated with changes in the dynamic spectrum at low strain, and a secondary micrometer-scale network that globally percolates at ~20 vol % associated with the Payne effect and electrical conductivity. A model is proposed with an elastomer dominated dynamic response described by Einstein–Smallwood behavior at high frequencies and small sizes and a filler network dominated response at low frequencies and large sizes. The nanoscale mesh size correlates with this transition in low strain dynamic response. The micrometer-scale network displays a gel-like dynamic response at very low frequencies and a corresponding gel-like structural scaling regime at large sizes. In conclusion, the hierarchical filler network is described by two crossover frequencies and associated relaxation times, τ* and τ cc , and two related structural scaling regimes.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Engineering Scale Simulation of Nonequilibrium Network Phases for Battery Electrolytes

According to the article, Diblock copolymers play an important role in the fabrication of battery materials and fuel cells. For these applications, one block provides mechanical stability, whereas the other is conducting. The application characteristics of the material critically depend on the morphology of the multicomponent material, and three-dimensional, percolating domains of the conducting domains are preferred. In this work, we investigate the nonequilibrium morphology of diblock copolymers after a quench from the disordered phase. After the spinodal self-assembly, we observe three-dimensionally percolating network structures for volume fractions, f ≥ 8/32, of the conducting component even if the equilibrium phases exhibit different percolation properties. We quantify the conductivity and tortuosity of these structures via a simple random-walk model and observe that the conductivity of the nonequilibrium structures is significantly smaller than that of the equilibrium phases. We also find large but finite-sized, fractal-like structures inside the morphology, which influence the transport properties. To explore the morphology on different scales and mitigate finite-size effects, we employ very large simulations with billions of particles. Our work demonstrates that for the prediction of bulk transport properties in these nonequilibrium morphologies it is necessary to study such large system sizes.

Polymer Science↗
DOE OSTI2019

Chain and Ion Dynamics in Precise Polyethylene Ionomers

In this paper, we analyze the dynamics from microsecond-long, atomistic molecular dynamics (MD) simulations of a series of precise poly(ethylene- co -acrylic acid) ionomers neutralized with lithium, with three different spacer lengths between acid groups on the ionomers and at two temperatures. At short times, the intermediate structure factor calculated from the MD simulations is in reasonable agreement with quasi-elastic neutron scattering data for partially neutralized ionomers. For ionomers that are 100% neutralized with lithium, the simulations reveal three dynamic processes in the chain dynamics. The fast process corresponds to hydration librations, the medium-time process corresponds to local conformational motions of the portions of the chains between ionic aggregates, and the long-time process corresponds to relaxation of the ionic aggregates. At 600 K, the dynamics are sufficiently fast to observe the early stages of lithium-ion motion and ionic aggregate rearrangements. In the partially neutralized ionomers with isolated ionic aggregates, the Li-ion-containing aggregates rearrange by a process of merging and breaking up, similar to what has been observed in coarse-grained (CG) simulations. In the 100% neutralized ionomers that contain percolated ionic aggregates, the chains remain pinned by the percolated aggregate at long times, but the lithium ions are able to move along the percolated aggregate. In this work, the ion dynamics are also qualitatively similar to those seen in previous CG simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗