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

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Effect of Polymer Topology on Microstructure, Segmental Dynamics, and Ionic Conductivity in PEO/PMMA-Based Solid Polymer Electrolytes

We report Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) have attracted much interest due to their high ionic conductivity resulting from inherently fast segmental dynamics and high salt solubility, yet they lack mechanical stability in their neat form. Blending PEO with another rigid, or high glass transition temperature, polymer is a versatile way to improve the mechanical stability; however, the ionic conductivity is strongly reduced due to slower segmental dynamics of highly interpenetrating linear polymer chains. In this work, we used model PEO/PMMA blend systems prepared with various well-defined PEO architectures (linear, stars, hyperbranched, and bottlebrushes) doped with lithium bis(trifluoromethane-sulfonyl)-imide (LiTFSI) and investigated, for the first time, the role of macromolecular architecture of PEO on crystallization, segmental dynamics, and ionic conductivity in the blends and electrolytes. The results suggest that room-temperature miscibility of these polymers can be dramatically extended by using nonlinear PEO in the blends instead of linear chains, which crystallize above 35 wt %. The broadband dielectric spectroscopy results revealed enhanced decoupling of PMMA and PEO segmental dynamics in compact branched architectures, which helps to achieve faster segmental motion of star PEO in glassy PMMA. This manifests as nearly three-fold higher ionic conductivity in these nonlinear blends compared to the conventional linear PEO/PMMA system. Regardless of the PEO architectures, the temperature dependence of ionic conductivity blends with PMMA and LiTFSI is well defined using the Vogel–Fulcher–Tammann mechanism, suggesting that ion transport is mainly affected by the segmental motion. The activation energy values decrease with the increasing ionic conductivity. Overall, our results show that macromolecular architecture can be a tool to decouple segmental dynamics and ion mobility to rationally design SPEs with improved performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Backbone Dynamics of Bottlebrush Polymers Studied by Neutron Scattering

Bottlebrush polymers have a versatile architecture that is highly customizable due to the combination of a linear backbone and side chains. As a result of the chemical tethering of the side chains, both parts cannot be easily be separated. Huge effort is seen regarding the dynamical behavior of the side chains or the entire bottlebrush polymer, whereas few studies are available considering the backbone. Here, isotopic labeling in combination with quasi-elastic neutron scattering was used to compare the dynamical behavior of the bottlebrush’s backbone with the side chain dynamics. Keeping the side chains deuterated, (h-PNB)- g -(d-PPO), leads to the scattering signal dominated by backbone dynamics, while the fully protonated sample, (h-PNB)- g -(h-PPO), gives side chain dynamics. Both results reveal slower dynamics associated with the backbone with less heterogeneity, as seen for the side chains. Additionally, a plasticizer effect for the backbone dynamics is confirmed by extracting the glass transition temperature and comparing it with pure linear PNB.

neutron scattering↗
DOE OSTI2025

Solvent Dynamics in Gel Polymer Electrolytes for Lithium–Sulfur Batteries

Li−sulfur (Li−S) batteries are promising as the next-generation energy storage technology but face challenges due to sluggish sulfur redox reaction (SRR) kinetics and a sulfur shuttling effect. While many studies have explored polycaprolactone (PCL)-based gel polymer electrolytes (GPEs) to address these issues, the influence of solvent properties, including dielectric constant (ϵ) and donor and acceptor numbers (DN and AN), remain unexplored despite their critical impact on performance and full-scale implementation. This study systematically compares three distinct electrolytes, dimethoxyethane (DME), dimethyl sulfoxide (DMSO), and tetraethylene glycol dimethyl ether (TEGDME)-paired with PCL, to correlate the varied solvent properties and their effects on the physical properties of the GPE, in terms of Li + transport and solvation, and polysulfide’s confinement. Among them, the DME-based GPE, with an intermediate DN, exhibited the lowest crystallinity (2.31%), highest ionic conductivity (7.49 mS/cm), and high Li + transference number (0.77). As a result, it achieved a specific capacity of 795 mAh/g sulfur and an average Coulombic efficiency of 97.5% after 120 cycles at C/5, outperforming its competitors. Operando Raman and UV−vis spectroscopy confirmed that PCL effectively confines long-chain polysulfides within its network, mitigating the shuttle effect and facilitating reversible polysulfide conversion. These findings demonstrate that GPEs with moderate DN values and balanced ϵ significantly enhance stability, extend cycle life, and improve rate performance for Li−S batteries. This work provides valuable insights into the design of advanced electrolyte systems for practical energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Structure, Dynamics, and Hydrogen Transport in Amorphous Polymers: An Analysis of the Interplay between Free Volume Element Distribution and Local Segmental Dynamics from Molecular Dynamics Simulations

Polymers are attractive membrane materials owing to their mechanical robustness and relatively inexpensive fabrication. An important indicator of membrane performance are free volume elements (FVE): microporous void spaces created by the inefficient packing of bulky groups along the polymer chain. FVEs tend to degrade over time, as polymer chains reorganize irreversibly. While it is widely accepted that polymer flexibility has an impact on membrane transport properties, the molecular nature of this impact is still not well understood. By the establishment of a correlation between local chain dynamics and the distribution of free volume elements (FVEs), penetrant transport can be regulated more efficiently in amorphous polymer membranes. In this work, we implement all-atom molecular dynamics (MD) simulations to explore the relationship between chain dynamics and free volume in three polymers with different levels of backbone flexibility: polymethylpentene (PMP), polystyrene (PS), and HAB-6FDA thermally rearranged polymer (TRP). We construct these polymers at different temperatures and examine how temperature impacts the FVE distribution and segmental mobility. Our analysis shows that chain segments near FVEs have higher mobility compared with the atoms in the bulk; the extent of this difference increases with chain flexibility. Increasing the chain flexibility by increasing the temperature results in a broader FVE distribution. Rigid polymers such as TRP show the most robust FVE distribution and are not significantly affected by the temperature change. To capture penetrant diffusion through the polymer matrix, hydrogen is inserted and the diffusion is measured at different temperatures; hydrogen mobility is influenced by the FVE structure and overall mobility of polymer chains. Lastly, at low temperatures, hydrogen mobility is influenced by void distribution, while at high temperatures, polymer dynamics dictate hydrogen transport.

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

Driving Force Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes

Here, we investigate the thermodynamic driving-force dependences of photoinduced charge separation (CS) and subsequent charge transfer dynamics in single-walled carbon nanotube (SWNT)–perylenediimide (PDI) donor–acceptor (D–A) superstructures. Pump–probe spectroscopy reveals that [SWNT (•+)n ]-(PDI –• ) n CS states form on an ∼100 fs time scale following photoexcitation; these dynamics are invariant across an ∼400 mV driving force range, indicating that SWNT hole polaron formation time scales are determined by nanotube lattice and solvent relaxation. These CS states feature SWNT hole polarons adjacent to (geminate) and nearby (nongeminate) PDI radical anions. Analysis of the free energy dependence for charge recombination (CR) of [SWNT •+ ] geminate -(PDI –• ) CS states highlights an ∼2 meV value for D–A electronic coupling (HAB) and ∼0.93 eV for the total reorganization energy (λ T ). A corresponding driving force dependence of the CR dynamics for [SWNT •+ ] nongeminate -(PDI –• ) CS states indicates a diminished H AB value (∼0.6 meV) and a larger λ T (∼1.1 eV), consistent with larger transfer distances. SWNT excitons that persist following photoinduced CS drive photooxidation of PDI –• components of [SWNT (•+)n ]-(PDI –• ) n CS states ( 1 SWNT* + PDI •– → PDI + SWNT •– ); this reaction manifests a significantly reduced λ T value (∼0.67 eV) as the initially prepared SWNT reduced state bears the character of a conduction band injected electron ([SWNT •– ] CB ). This reaction thus gives rise to relaxed, nongeminate SWNT electron and hole polarons on the same nanotube; these polarons react on a 10 2 ps time scale independent of the electronic structure of these SWNT-PDI superstructures.

anions↗
DOE OSTI2020

Collaborative Research: Polymer Macrocycles: A novel topology to control dynamics of rubbery materials

Understanding the dynamics of polymers of different topologies is an important field of study and one of the most important unanswered questions in this field is "how do circular polymers move," particularly in the melt state. New information suggests that molecular topology, specifically circular rings, impacts the response of materials in nanometer- scale confinement. The work performed here tackles these subjects through a collaboration in which specialists in polymer synthesis, polymer rheology and scattering methods, and in the physics of nanoconfinement work together to investigate the thermophysical behavior of circular macromolecules. The project goals are to use a novel synthesis method of "green" oxidative polymerization to produce high purity macrocycles and to investigate their linear viscoelastic behavior in order to fully characterize the dynamics of circular macromolecules to sizes that correspond to linear molecule entanglement densities higher than previously obtainable with synthetic polymers. Chemical chain end characterization and critical edge fractionation coupled with direct visualization of the prepared polymers through the use of polymer amplification methods are proposed in order to quantify the numbers of circular and linear molecules in each sample. The study of the linear viscoelastic response of blends of linear and circular molecules is also to be undertaken in the project. Nonlinear viscoelastic measurements, including extensional viscosity, are to be made. Strong differences in behavior between linear chains and circular ones also provides an important opportunity for new technology to break the "magic triangle" for tires: it is believed that improving one of the three key attributes - traction, wear, rolling resistance - necessarily sacrifices at least one of the others. Rubber made from cyclic polymers has the potential to break out of this triangle by reducing the so-called Payne effect in reinforced rubbers because circular macromolecules are less sensitive to nanoconfinement than their linear counterparts. The work has as one objective to characterize the impact of nanoconfinement on the behavior of large circular macromolecules. In addition, the dynamics of carbon black filled circular macromolecules are to be studied to test the hypothesis that the resulting rubbery materials will exhibit a reduced Payne effect.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Understanding the Structure and Dynamics of Conjugated Polymers by Advancing Deuteration Chemistry and Neutron Scattering (Final Report)

The overarching goal of the proposed work was to set up a partnership between the University of Southern Mississippi (USM) and Oak Ridge National Laboratory (ORNL) to develop novel approaches to measure the backbone rigidity of conjugated polymers (CPs) and understand the critical role of sidechains on the backbone conformation and the materials macroscopic property. The backbone rigidity greatly influences the electronic properties of CPs, which ultimately determines the functionality and performance of these materials. Improvements in the electronic properties of CPs would allow for enhanced charge transport in semiconductor devices, improved photovoltaic performance, recycling of waste heat in thermoelectrics, and discovery of new phenomena that will enable the next generation of energy technologies. Although significant progress has been made to optimize the optical and electronic properties of CPs, largely through Edisonian methodologies, it remains a challenge to experimentally characterize conjugated backbone conformation (chain rigidity, torsion, planarity, and short-range order) and relate these to the fundamental optical and electronic properties (electronic coupling, charge transport, etc.). This has left fundamental gaps in our knowledge of the most basic structure/property relationships within these systems, precluded the study of fundamental physical phenomena, and constrained the design and realization of new electronic and device functionalities. Thus, the major goal of this work is to use novel deuteration methodologies via systematic synthetic approaches, and neutron scattering techniques to comprehensively characterize the structural and dynamic properties of CPs in contrast-matching solvents. Our work would, for the first time, elucidate the relationship between backbone rigidity and macroscopic properties. They will also allow a rational formulation of design principles for next-generation CPs that are resilient to disorder through precise control of the delocalized electrons along the polymer backbone. Overall, this project will advance our understanding of the structure, dynamics, and fundamental physics of these materials, which is crucial for enabling the prediction, design, control, and manipulation of current and emerging material electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.

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

Optoelectronic polymer memristors with dynamic control for power-efficient in-sensor edge computing

Abstract As the demand for edge platforms in artificial intelligence increases, including mobile devices and security applications, the surge in data influx into edge devices often triggers interference and suboptimal decision-making. There is a pressing need for solutions emphasizing low power consumption and cost-effectiveness. In-sensor computing systems employing memristors face challenges in optimizing energy efficiency and streamlining manufacturing due to the necessity for multiple physical processing components. Here, we introduce low-power organic optoelectronic memristors with synergistic optical and mV-level electrical tunable operation for a dynamic “control-on-demand” architecture. Integrating signal sensing, featuring, and processing within the same memristors enables the realization of each in-sensor analogue reservoir computing module, and minimizes circuit integration complexity. The system achieves 97.15% fingerprint recognition accuracy while maintaining a minimal reservoir size and ultra-low energy consumption. Furthermore, we leverage wafer-scale solution techniques and flexible substrates for optimal memristor fabrication. By centralizing core functionalities on the same in-sensor platform, we propose a resilient and adaptable framework for energy-efficient and economical edge computing.

Optics↗
NASA NTRS1995

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

Jaffe, Richard↗