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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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Ultra-selective CANAL Polymers for Hydrogen-based Membrane Separations after Long-Term Aging

Hydrogen is a critically important molecule in the chemicals and energy industries, driving the need for efficient purification technologies such as membrane-based separations. However, polymer membranes often suffer from physical aging, leading to decreased gas permeability over time. This study leverages the unique aging behavior of contorted microporous polymers, synthesized via catalytic arene-norbornene annulation (CANAL) polymerization, to enhance molecular sieving for H 2 separations. While prior studies demonstrated a 1000% increase in H 2 /CH 4 selectivity with minimal permeability loss over 150 days, we extend this investigation to hyperaged (∼1 year) CANAL polymers and evaluate their performance under various conditions of industrial relevance. We report a remarkable 6100% increase in H 2 /CH 4 selectivity and a 2400% improvement in H 2 /N 2 selectivity, with only a 55% decline in H 2 permeability. These membranes exhibit excellent long-term stability in binary and ternary gas mixtures and at elevated temperatures. Additionally, extended aging enhances H 2 /CO 2 selectivity beyond the 2008 upper bound due to improved size-sieving. High-temperature permeation experiments and grand canonical Monte Carlo simulations reveal that H 2 permeability increases from 570 to 3500 barrer as the temperature rises from 35 °C to 190 °C, while H 2 /CO 2 selectivity declines from 14 to 3 due to the higher diffusion activation energy of CO 2 . Despite this tradeoff, hyperaged CANAL membranes maintain performance beyond the 200 °C upper bound, having selectivity–permeability performance comparable to many state-of-the-art membranes for H 2 /CO 2 separations. As a result, this study highlights the robustness and industrial viability of ultra-selective CANAL polymers for hydrogen purification, contributing to advancements in clean energy and sustainable separation technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Molecular-level insights into structure and dynamics in ionic liquids and polymer gel electrolytes

We report designing new electrolytes requires a better understanding of the correlation between their transport properties and their molecular structure. In this work, we present a detailed study of ionic liquids and polymer gel electrolytes probing their structure and dynamics by nuclear magnetic resonance (NMR) spectroscopy. In particular, ammonium- and phosphonium-based ionic liquids (ILs) are combined with different LiTFSI concentrations, and then with different ratios of poly(methylmethacrylate) polymer. The temperature dependence of self-diffusion coefficients of mobile species, D Li+ , D TFSI- and D P4441+ or D N4441+ , measured by pulsed field gradient (PFG) NMR spectroscopy obeys the Arrhenius equation. Diffusivity of [P4441][TFSI] ILs is found to be greater than those of the [N4441][TFSI] ILs in both liquid and gel electrolytes. Solid state NMR experiments including 13 C and 19 F MAS, 13 C{ 19 F}, 13 C{ 1 H} CPMAS probe the local structure and molecular-level interactions between ions and polymer in gel electrolytes, particularly for samples with higher PMMA content (≥25 wt%). Finally, the fast field cycling relaxometry has been used to unveil the rotational and translational dynamics of P4441 + or N4441 + and TFSI - by measuring 1 H and 19 F R 1 relaxation rate profiles at different temperatures. A comprehensive NMR analysis including relaxation studies at low magnetic field provides decisive new insights regarding the formation of ionic clusters and the interaction of ions with the polymer chain in the case of the gel electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Connecting radiation-driven changes in structural, thermal, and mechanical properties in several medical device polymers

Stemming from security threats and shortages in supply, a recent push has emerged to develop alternatives to radioisotope Cobalt-60 gamma radiation for sterilization of polymeric medical products, including electron beam (e-beam) and X-ray machine-based sources. However, before large-scale implementation, the effects of these non-isotope-based methods must be thoroughly investigated from several perspectives, involving their potential detrimental effects on the structural, thermal, and mechanical properties of polymers in medical devices. This paper investigates such effects in commonly used medical device polymers, including polypropylene homopolymer (PPH), polyolefin elastomer (POE), low-density polyethylene (LDPE), acrylonitrile butadiene styrene (ABS), and chlorobutyl rubber (CIIR). To connect radiation-driven changes in polymer structural and thermal properties and corresponding changes in mechanical properties, several characterization techniques were utilized, including gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). We found that the tensile strength of X-ray irradiated PPH, as well as X-ray, e-beam, and gamma irradiated CIIR decreases due to chain scission, which is corroborated by GPC and DMA. The GPC results of LDPE suggest chain scission, but interestingly without a corresponding decline in tensile strength. By comparison, POE and ABS appear to undergo further crosslinking with increasing irradiation dose, which generally strengthens them. Importantly, in the vast majority of the cases, there were small to no changes in properties upon changing radiation technologies (at a given dose), i.e., no radiation source dependence. However, in a few specific cases, radiation method dependencies did arise, for instance, in terms of the molecular weight of PPH being significantly increased upon X-ray irradiation, while the melting temperature, glass transition temperature, and elongation at break reduced compared to gamma. Overall, this study provides valuable insight into radiation-driven chemical and structural changes in polymers that produce changes in physical and functional properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermo-mechanical deterioration and molecular degradation of 3D-printed methacrylate-based polymer in various chemical environments

The advancement of additive manufacturing (AM) has accelerated the development of stereolithographic (SLA) photo-curable resins, particularly methacrylate-based polymers, due to the ability to their high-resolution, robust mechanical properties, and suitability. However, their long-term performance in chemical environments remains poorly understood. This study investigates the extent and mechanisms of degradation on an SLA-printed methacrylate-based polymer subjected to various chemicals, including polar and non-polar solvents, as well as strongly acidic aqueous solutions over a 12-week accelerated aging period. A comprehensive analytical approach incorporating swelling kinetics, surface morphology, tensile and dynamic mechanical analysis (DMA), Fourier-transform infrared (FTIR) spectroscopy, and mass spectrometry (MS) was employed to characterize chemical absorption, structural integrity, and leached products. Results reveal that degradation severity is governed by both the polarity and reactivity of the chemical environment. Notably, exposure to 6 mol L -1 HNO₃ induced the most severe deterioration, with over threefold higher swelling compared to other media, and significant reductions in tensile strength, tensile modulus, and glass transition temperature (T g ). In contrast, specimens aged in non-polar solvents (xylene and dodecane) exhibited negligible chemical interaction and retained mechanical performance. FTIR and MS analyses identified acid-catalyzed hydrolysis of ester groups as prominent degradation pathways in acidic media, while diffusion-controlled plasticization prevailed in polar solvents. Furthermore, this study provides valuable insights into the chemical stability of SLA-printed polymers and develops predictive degradation profiles that are crucial for designing durable polymer systems for advanced industrial use.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Functional stimuli-responsive polymers on micro- and nano-patterned interfaces

Micro- and nano-patterned surfaces offer precise control over morphology and chemical composition, enhancing the stability, durability, and functionality of coating materials. When combined with stimuli-responsive polymers, these surfaces gain dynamic adaptability, enabling reversible binding, reusable sensing, and selective molecular capture. Furthermore, while recent review articles have explored various aspects of stimuli-responsive materials, from hydrogel patterns for bioanalytical applications to shape-morphing hydrogels for soft robotics and sensors, a comprehensive review focused on the integration of smart polymers with micro- or nano-patterned interfaces remains absent. This review addresses key surface patterning techniques, including soft lithography, colloidal lithography, and polymer brush photolithography, as well as advances in surface-initiated polymerization methods, such as surface-initiated controlled radical polymerization (SI-CRP). In addition, we discuss recent progress in integrating stimuli-responsive polymers with patterned surfaces to create advanced, functional materials.

Colloidal lithography↗
DOE OSTI2025

Isomerization kinetics of azobenzene crosslinked to a liquid crystal polymer network

Azobenzene is an important chromophore having numerous applications that are a direct implication of its ability to change shape upon irradiation with a suitable wavelength. Here, in this study, photoisomerization kinetics of a diacrylate azobenzene molecule (A3MA) cross-linked to a liquid crystal polymer network (LCN) is investigated. Isomerization experiments were conducted on planar LCN thin films with varying cross-linking densities for a fixed azobenzene concentration. The experiments were conducted at approximately 26 °C, which is significantly below each film’s glass transition temperature. The forward trans-cis and reverse cis-trans isomerization slows down in crosslinked azobenzene liquid crystal polymer networks (ALCNs) as compared to a solution and an uncrosslinked polymer mixture. The observed slowdown is due to the reduction in the free volume and increased steric hindrances with an increase in crosslinking. A single-term first-order kinetics rate equation is known to describe the isomerization kinetics in solutions or uncrosslinked mixtures while the same form fails to represent the reaction kinetics in moderate to highly cross-linked ALCNs. Our results for the first time indicate that a two-term first-order reaction rate is an accurate way to describe the forward trans-cis and reverse thermal cis-trans isomerization in crosslinked azobenzene liquid crystal polymer networks. In addition, the effect of film thickness and incident intensities on the reaction kinetics is investigated. Finally, the two-term isomerization kinetics is incorporated into a finite element photo-chemo-mechanical model to reveal the consequent slowdown in the actuation response of ALCN films. The current findings will be of particular interest to theoreticians and experimentalists alike, for it will help predict and understand accurately the responses of azobenzene-based coatings, and actuators and may have potential applications in underwater soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

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↗
DOE OSTI2025

A solvent-targeted recovery and precipitation scheme for the recycling of up to ten polymers from post-industrial mixed plastic waste

Solvent-Targeted Recovery and Precipitation (STRAP TM ) separates polymers within a plastic waste stream by selective dissolution. In this work, the STRAP framework, which combines computational modeling and experiments, was applied to develop a series of steps to separate up to 10 polymers from post-industrial mixed plastic waste (MPW) and the main components recovered were LDPE, HDPE, and PET. The STRAP steps were initially demonstrated with a physical polymer mixture containing LDPE, HDPE, PS, PVC, EVOH, PET, PP, PA6, PA66, and PA66/6, in which recoveries of 89% or higher were achieved for each polymer. Furthermore, this paper demonstrates a solvent selection approach that can be applied to separate unknown plastics materials into purer components.

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

Origin of rate limitations in solid-state polymer batteries from constrained segmental dynamics within the cathode

Currently, one of the key challenges preventing the wide commercialization of polymer-based solid-state batteries is achieving high-rate capabilities. This work unravels chain structure and segmental dynamics in a polymer-based composite cathode consisting of LiFePO 4 (LFP), carbon, and poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide. Small-angle neutron scattering (SANS) data reveal that PEO chains are adsorbed on the surface of LFP particles during slurry processing to make the composite electrode. The strong interaction between LFP and PEO chains leads to greatly reduced segmental dynamics of PEO, as discovered by quasi-elastic neutron scattering (QENS). The reduced segmental dynamics results in 70% decreased Li + mobility of the polymer electrolyte in the composite cathode. The combined SANS and QENS study indicates that one of the key bottlenecks that limits the rate performance of PEO-based polymer batteries originates from molecular interactions within the cathode.

25 ENERGY STORAGE↗
DOE OSTI2021

Polymer Coatings on Virus-like Particle Nanoreactors at Low Ionic Strength—Charge Reversal and Substrate Access

Virus-like particles (VLPs) are a class of biomaterials which serve as platforms for achieving the desired functionality through interior and exterior modifications. Through ionic strength-mediated electrostatic interactions, VLPs have been assembled into hierarchically ordered materials. This work builds on predictive models to prepare polymer-coated VLP dusters at very low ionic strength. Zeta potential measurements showed that the clusters carried a strongly positive charge, a complete charge reversal from the VLP building block. SAXS analysis confirmed polymer adsorption onto the VLP exterior. Furthermore, we then studied the activity of an encapsulated enzyme toward small molecular and macromolecular substrates to determine the effect of each component of the hierarchically assembled material. We found that while encapsulation and polymer coating did not have a large effect on access to the enzyme by its native, small molecular substrate, substrate modification with a macromolecule caused the polymer coating and encapsulation to affect the access to the enzyme.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers

Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F 4 TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F 4 TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chain nonbond energy is lower in the P3MEET:F 4 TCNQ mixture, suggesting more favorable dopant–side-chain interaction, which is a factor in improving the thermal stability of a polymer/dopant pair. Our results reveal that additional factors such as polymer ionization energy and side-chain–dopant interaction should be taken into account for the design of thermally stable, highly conductive polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Partial Solvation of Lithium Ions Enhances Conductivity in a Nanophase-Separated Polymer Electrolyte

In this study, we demonstrate that a multiblock lithium-ion-conducting polymer can be swollen with ethylene carbonate solvent to increase the conductivity relative to the dry polymer material by nearly 4 orders of magnitude. This increase is due to the partial solvation of lithium ions by ethylene carbonate, which leads to Li + diffusion along the solvent–polymer interface. This differs from the vehicular transport mechanism for lithium ions in pure solvent. We use a combination of broadband dielectric spectroscopy, X-ray scattering, and all-atom molecular dynamics simulations to probe the effect of the solvent on the polymer morphology and to elucidate the mechanism of lithium ion transport.

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

Transferring a Molecular Foundation Model for Polymer Property Predictions

Transformer-based large language models have remarkable potential to accelerate design optimization for applications such as drug development and material discovery. Self-supervised pretraining of transformer models requires large-scale data sets, which are often sparsely populated in topical areas such as polymer science. Further, state-of-the-art approaches for polymers conduct data augmentation to generate additional samples but unavoidably incur extra computational costs. In contrast, large-scale open-source data sets are available for small molecules and provide a potential solution to data scarcity through transfer learning. In this work, we show that using transformers pretrained on small molecules and fine-tuned on polymer properties achieves comparable accuracy to those trained on augmented polymer data sets for a series of benchmark prediction tasks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Off-Lattice Markov Chain Monte Carlo Simulations of Mechanically Driven Polymers

Here, we develop off-lattice simulations of semiflexible polymer chains subjected to applied mechanical forces by using Markov Chain Monte Carlo. Our approach models the polymer as a chain of fixed length bonds, with configurations updated through adaptive nonlocal Monte Carlo moves. This proposed method enables precise calculation of a polymer’s response to a wide range of mechanical forces, which traditional on-lattice models cannot achieve. Our approach has shown excellent agreement with theoretical predictions of persistence length and end-to-end distance in quiescent states as well as stretching distances under tension. Moreover, our model eliminates the orientational bias present in on-lattice models, which significantly impacts calculations such as the scattering function, a crucial technique for revealing the polymer conformation.

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

Dynamical Ion Correlations in Polymer and Membrane Electrolytes: Recent Advances and Open Questions

Ion transport in polymer and membrane electrolytes is often described using uncorrelated models like the Nernst–Einstein (NE) approximation, which link conductivity, transference number, and salt diffusivity to individual ion mobilities. However, growing evidence shows that dynamical ion correlations─arising from ion pairing, polymer-mediated coupling, confinement, and electrostatic interactions─can substantially alter macroscopic transport properties. The Onsager transport formalism offers a rigorous framework to quantify these effects via cross-correlated ionic displacements. This Perspective highlights how such correlations manifest across dry and hydrated systems, including salt-doped polymers, block copolymers, hydrogels, and ion-exchange membranes. Here, we examine key physical origins, the influence of salt chemistry and polymer structure, and open questions in measuring and controlling correlated motion. Embracing correlation-aware design enables new pathways to optimize conductivity, transference number, and selectivity─shifting the focus from individual ion mobility to engineered collective dynamics for next-generation electrolytes in energy storage and separations.

Charge transport↗
DOE OSTI2021

Role of Molecular Architecture on Ion Transport in Ethylene oxide-Based Polymer Electrolytes

This work aims to develop a detailed mechanistic understanding of the role of a graft polymer architecture on lithium ion (Li + ) transport in poly(ethylene oxide)-based polymer electrolytes. Specifically, we compare Li + transport in poly-(ethylene oxide) (PEO) versus poly(oligo oxyethylene methacrylate) (POEM) polymers doped with lithium bis( trifluoromethanesulfonyl) (LiTFSI) salts, using both experimental electrochemical characterization and molecular dynamics (MD) simulations. Furthermore, our results indicate that POEM exhibits a range of relaxation processes that cannot be interpreted solely in terms of glass-transition temperature (T g ) effects. Due to its side-chain architecture, the segmental relaxation of POEM is nonuniform across ether oxygens (EOs) and shows a more pronounced sensitivity to temperature above T g compared to PEO. Moreover, POEM also exhibits a nonuniform Li + coordination behavior, in which Li + is primarily solvated by two different chains in POEM, compared to a single chain in PEO. Li + transport in POEM occurs via two events with distinct characteristic times: a fast intrachain hopping along side chains and a slow interchain hopping between side chains. Taken together, the relaxation processes and ion transport mechanisms identified in POEM provide useful insights into design of more effective solid polymer electrolytes.

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

Probing Nanorod Assembly and Dynamics in Polymer Nanocomposites in Equilibrium and Shear

Coarse-grained molecular dynamics simulations are used to examine the structure and dynamics of nanorod assemblies in polymer melts under equilibrium and simple shear. We show that as the concentration of nanorods increases, there is a transition from an isotropic phase to a two-phase region in which the nanorods phase separate into a dilute phase and dense bundles of hexagonally packed nanorods. The onset of the two-phase region is below that predicted by Onsager theory, which we attribute to an effective increase in the diameter of nanorods due to a layer of polymer bound to the rod surfaces. Equilibrium simulations show that increasing polymer chain length N enhances nanorod bundling at fixed nanorod concentration. Simulations of systems undergoing simple shear show that flow enhances nanorod alignment and bundling relative to those of equilibrium systems with similar properties. Finally, simulations reveal that increasing nanorod length enhances nanorod alignment under shear at equivalent shear rates but not at equivalent Péclet numbers. Overall, our simulations highlight that polymer matrix-nanorod attraction (i.e., chemistry), shear rate, and matrix chain length are desirable design variables to control the structure of nanorod-containing soft materials under simple shear.

diffusion↗
DOE OSTI2026

Cross-Linker Selection Controls Glass Transition Elevation or Reduction in Dynamic Covalently Bonded Polymer Networks

Introducing cross-links is a powerful approach to improve polymeric material performance relevant to controlling viscoelasticity, thermal and creep resistance, degradability, and efficient membrane separations. The chemically specific glass transition temperature T g is of fundamental importance in determining the time scales of key dynamical processes and physical state of the material in such applications. Here, we study experimentally how the introduction of relatively large cross-linking molecules in slowly exchanging dynamic bond-forming polymers (vitrimers) impacts vitrification for diverse polymer chemistries and a wide range of cross-link fractions. We find T g can increase, decrease, or even remain essentially unchanged, in qualitative contrast to the generic elevation of T g in traditional permanent polymer networks. We formulate an effective terpolymer network model to understand this rich behavior, which emerges as a consequence of a competition between pure cross-linking and generalized plasticization effects. The latter is associated with the tunable cross-linker size and intrinsic dynamic mobility that can offset slowing down due to traditional permanent cross-linking constraints. Here, a new strategy for functional polymer network design is suggested based on adjusting the relative importance of the two competing physical effects, which potentially can significantly enhance energy savings in applications while retaining other intrinsic properties germane to advanced materials performance.

Copolymers↗