Search NASA⌕ Search

SEARCH · Search NASA

Results for “polymer physics”

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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Solution-Deposited and Patternable Conductive Polymer Thin-Film Electrodes for Microbial Bioelectronics

Microbial bioelectronic devices integrate naturally occurring or synthetically engineered electroactive microbes with microelectronics. These devices have a broad range of potential applications, but engineering the biotic–abiotic interface for biocompatibility, adhesion, electron transfer, and maximum surface area remains a challenge. Prior approaches to interface modification lack simple processability, the ability to pattern the materials, and/or a significant enhancement in currents. We report a novel conductive polymer coating that significantly enhances current densities relative to unmodified electrodes in microbial bioelectronics is reported. The coating is based on a blend of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) crosslinked with poly(2-hydroxyethylacrylate) (PHEA) along with a thin polydopamine (PDA) layer for adhesion to an underlying indium tin oxide (ITO) electrode. When used as an interface layer with the current-producing bacterium Shewanella oneidensis MR-1, this material produces a 178-fold increase in the current density compared to unmodified electrodes, a current gain that is higher than previously reported thin-film 2D coatings and 3D conductive polymer coatings. The chemistry, morphology, and electronic properties of the coatings are characterized and the implementation of these coated electrodes for use in microbial fuel cells, multiplexed bioelectronic devices, and organic electrochemical transistor based microbial sensors are demonstrated. It is envisioned that this simple coating will advance the development of microbial bioelectronic devices.

patterned bioelectronics↗
DOE OSTI2020

Mechanochemical synthesis of pillar[5]quinone derived multi-microporous organic polymers for radioactive organic iodide capture and storage

The incorporation of supramolecular macrocycles into porous organic polymers may endow the material with enhanced uptake of specific guests through host–guest interactions. Here we report a solvent and catalyst-free mechanochemical synthesis of pillar[5]quinone (P5Q) derived multi-microporous organic polymers with hydrophenazine linkages (MHP-P5Q), which show a unique 3-step N 2 adsorption isotherm. In comparison with analogous microporous hydrophenazine-linked organic polymers (MHPs) obtained using simple twofold benzoquinones, MHP-P5Q is demonstrated to have a superior performance in radioactive iodomethane (CH 3 I) capture and storage. Mechanistic studies show that the rigid pillar[5]arene cavity has additional binding sites though host–guest interactions as well as the halogen bond (-I···N = C-) and chemical adsorption in the multi-microporous MHP-P5Q mainly account for the rapid and high-capacity adsorption and long-term storage of CH 3 I.

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

Diffusion power spectra as a window into dynamic materials architecture

Chemical recycling of commodity and specialty polymers presents a multifaceted challenge for industrial societies. On one hand, macromolecular architectures must be engineered to yield durable products that, on the other hand, rapidly deconstruct to recyclable monomers under pre-determined conditions. Polymer deconstruction is a chemical process that requires deep understanding of molecular reactivity in heterogeneous media, where porous material architectures evolve in both space and time. To build this understanding, we develop herein experimental and analytical methods describing sets of diffusive eigenmodes that exist within time-varying, non-Euclidean boundary conditions, a situation commonly encountered in the reactive deconstruction of polymers where chain fragments splay, alter their local dynamics, and evolve in their confinement of reacting media. Diffusion power spectra, discerned experimentally by NMR, yield polymer and solvent frequency-domain velocity autocorrelation functions that are analyzed in the context of physical models for chemical reactions parameterized with fractal mathematics. The results connect local motion in polymers to chemical reactivity during acidolysis of circular elastomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tuning dispersity of linear polymers and polymeric brushes grown from nanoparticles by atom transfer radical polymerization

Molecular weight distribution imposes considerable influence on the properties of polymers, making it an important parameter, impacting morphology and structural behavior of polymeric materials. Atom transfer radical polymerization (ATRP) has established itself as a powerful tool to prepare polymers with predetermined molecular weight, preserved chain-end functionality, and low dispersity. More recently, ATRP has also been shown to provide a means to deliberately broaden molecular weight distributions, and, via retaining living chain-ends, to enable the formation of block copolymers with designed block dispersity, featuring new microstructures and potentially attractive properties. Here, similar methodologies have been developed to facilitate tuning of the dispersity of polymeric brushes grown from nanoparticles thus resulting in hybrid materials with enhanced fracture toughness and high inorganic content. Recent advances have given access to brush architectures comprised of uni- and bimodal block copolymers with unique morphologies along with interesting mechanical, thermal, and optical properties.

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

Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. Here we present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthetic biodegradable polyhydroxyalkanoates (PHAs): Recent advances and future challenges

This article reviews the advances made over the past five decades of research in developing effective chemocatalytic pathways to synthesize polyhydroxyalkanoates (PHAs), a prominent class of biodegradable polyesters found in nature and considered as sustainable alternatives to petroleum-based non-degradable plastics. Focused in this review are recent efforts that seek to address the key challenges facing the biosynthetic routes by taking advantage of precision in synthesis, expedient tunability in polymer stereomicrostructures and structures of monomers and molecular catalysts, as well as scalability and speed in polymer production that chemical catalysis can offer. This article is organized by poly(3-hydroxybutyrate) (P3HB) stereomicrostructures (tacticities), from isotactic to syndiotactic to atactic P3HB materials, followed by other PHA homopolymers and copolymers. Under each type of stereochemically defined PHAs, monomers, catalysts, and polymerizations employed for the synthesis, as well as mechanistic aspects when possible, are described. Next, recent advances in expanding the PHA scope and developing functionalized, uncommon or unnatural PHAs, inaccessible by biological methods, especially block and stereoblock or stereosequenced PHAs, are highlighted in their synthetic methods and advanced materials properties. As a result, four key remaining challenges, and thus corresponding future directions directed at addressing those challenges, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermoresponsive polymer assemblies via variable temperature liquid-phase transmission electron microscopy and small angle X-ray scattering

Abstract Herein, phase transitions of a class of thermally-responsive polymers, namely a homopolymer, diblock, and triblock copolymer, were studied to gain mechanistic insight into nanoscale assembly dynamics via variable temperature liquid-cell transmission electron microscopy (VT-LCTEM) correlated with variable temperature small angle X-ray scattering (VT-SAXS). We study thermoresponsive poly(diethylene glycol methyl ether methacrylate) (PDEGMA)-based block copolymers and mitigate sample damage by screening electron flux and solvent conditions during LCTEM and by evaluating polymer survival via post-mortem matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). Our multimodal approach, utilizing VT-LCTEM with MS validation and VT-SAXS, is generalizable across polymeric systems and can be used to directly image solvated nanoscale structures and thermally-induced transitions. Our strategy of correlating VT-SAXS with VT-LCTEM provided direct insight into transient nanoscale intermediates formed during the thermally-triggered morphological transformation of a PDEGMA-based triblock. Notably, we observed the temperature-triggered formation and slow relaxation of core-shell particles with complex microphase separation in the core by both VT-SAXS and VT-LCTEM.

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

Polymers in Deep Eutectic Solvents

The project investigated the behavior of polymers in ionic liquids such as deep eutectic solvents using an array of techniques. These included the development of atomistic force fields, coarse graining these force fields to the united atom level, large scale molecular dynamics (MD) simulations using new thermostat algorithms, and machine learning (ML) methods for the phase behavior. The project demonstrated the feasibility and accuracy of first principles force fields for ionic liquids, deep-eutectic solvents, and urea-water mixtures. A novel hierarchical coarse graining method was then used to develop accurate and efficient united-atom models, using which microsecond simulations were performed for polymers in ionic liquids. These simulations were in quantitative agreement with experiment, thus resolving previous controversies. Methods were also developed to obtain the potential of mean force between complex ions in solution. Finally, supervised ML methods were developed for the phase behavior of polymers in ionic liquids.

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

Cu-Catalyzed Atom Transfer Radical Polymerization: The Effect of Cocatalysts

Atom transfer radical polymerization (ATRP) is one of the most powerful methods to prepare well-defined (co)polymers. Cu-catalyzed ATRP methods are most commonly used because of the excellent control and tunable catalytic activities via ligand functionalization. This minireview summarizes the development of Cu-catalyzed ATRP in the presence of cocatalysts, which are used to regenerate Cu I complex activators during polymerizations. Fundamentals of Cu-based ATRP catalysts are first introduced, followed by the discussion of different types of cocatalysts in different Cu-catalyzed ATRP methods. Recent developments of photochemical cocatalysts for oxygen-tolerant ATRP and ATRP using long-wavelength irradiation are highlighted, which significantly expand the applications of Cu-catalyzed ATRP. Methods to study the properties of cocatalysts and their roles in Cu-catalyzed ATRP are discussed, with an outlook for the future development of cocatalysts.

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

Sequence Design of Random Heteropolymers as Protein Mimics

Random heteropolymers (RHPs) have been computationally designed and experimentally shown to recapitulate protein-like phase behavior and function. However, unlike proteins, RHP sequences are only statistically defined and cannot be sequenced. Recent developments in reversible-deactivation radical polymerization allowed simulated polymer sequences based on the well-established Mayo–Lewis equation to more accurately reflect ground-truth sequences that are experimentally synthesized. This led to opportunities to perform bioinformatics-inspired analysis on simulated sequences to guide the design, synthesis, and interpretation of RHPs. We compared batches on the order of 10000 simulated RHP sequences that vary by synthetically controllable and measurable RHP characteristics such as chemical heterogeneity and average degree of polymerization. Our analysis spans across 3 levels: segments along a single chain, sequences within a batch, and batch-averaged statistics. We discuss simulator fidelity and highlight the importance of robust segment definition. Examples are presented that demonstrate the use of simulated sequence analysis for in-silico iterative design to mimic protein hydrophobic/hydrophilic segment distributions in RHPs and compare RHP and protein sequence segments to explain experimental results of RHPs that mimic protein function. To facilitate the community use of this workflow, the simulator and analysis modules have been made available through an open source toolkit, the RHPapp.

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

Inter-Oligomer Interaction Influence on Photoluminescence in Cis-Polyacetylene Semiconductor Materials

Semiconducting conjugated polymers (CPs) are pivotal in advancing organic electronics, offering tunable properties for solar cells and field-effect transistors. Here, we carry out first-principle calculations to study individual cis-polyacetylene (cis-PA) oligomers and their ensembles. The ground electronic structures are obtained using density functional theory (DFT), and excited state dynamics are explored by computing nonadiabatic couplings (NACs) between electronic and nuclear degrees of freedom. We compute the nonradiative relaxation of charge carriers and photoluminescence (PL) using the Redfield theory. Our findings show that electrons relax faster than holes. The ensemble of oligomers shows faster relaxation compared to the single oligomer. The calculated PL spectra show features from both interband and intraband transitions. The ensemble shows broader line widths, redshift of transition energies, and lower intensities compared to the single oligomer. This comparative study suggests that the dispersion forces and orbital hybridizations between chains are the leading contributors to the variation in PL. It provides insights into the fundamental behaviors of CPs and the molecular-level understanding for the design of more efficient optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Design, synthesis and characterization of fused bithiazole- and dithiophene-based low bandgap thienylenevinylene copolymers

The structural rigidity of fused units in the polymer backbone, in addition to the resulting stabilizing effect of the quinoidal structure, and tunable electronic properties have played a key role in promoting highly-ordered π-stacking moieties, exhibiting promising charge carrier mobilities. The electron-deficient thiazole moiety shows high planarity and effective π–π stacking, which leads to the reduction in the energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), and ideally enhances the electron charge mobility. Four heterocycle-based monomers BTzS, BTzSe, DTS, and DTG based on fused bithiazole and dithiophene units incorporated with sulfur, selenium, silicon, and germanium as the bridging atoms were synthesized and characterized. Here, the monomers were copolymerized with the electron-rich alkylated thienylenevinylene (TV) unit to afford copolymers P1–P4. The thermal, optical, and electrochemical properties and crystallinity of the copolymers were thoroughly investigated. Extensive OFET device optimization using different solvents and annealing temperatures resulted in the best charge mobility of 0.09 cm2 V –1 s –1 for the electron-deficient bithiazole BTzS copolymer P1 and 0.36 cm2 V –1 s –1 for the DTS copolymer P3.

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

Accelerated Self-Healing and Property Recovery in Brush Particle Solids Featuring Brush Dispersity

Brush particles, hybrid materials consisting of polymer chains tethered to particle surfaces, offer tunable properties that make them promising candidates for advanced functional materials. This study investigated the role of chain dispersity in the viscoelastic self-healing of poly (methyl acrylate) (PMA)-based brush particle solids. Increasing the molecular weight dispersity of grafted chains significantly enhanced both strain-to-fracture and toughness of brush particle solids, while the elastic modulus and glass transition temperature were independent of chain dispersity. Cut-and-adhere testing revealed a significant acceleration of the rate of toughness recovery in high-dispersity systems as compared to low-dispersity analogs for which toughness recovery markedly lagged the recovery of Young’s modulus. The results suggest that structure and property recovery in brush particle solids are sensitive to the dynamical heterogeneity of brush canopies and highlight the role of molecular weight dispersity as a design parameter to enable hybrid materials with advanced self-healing ability.

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

Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds

Currently, there are few examples of circularly recyclable polymers with all-carbon backbones, probably owing to the challenge of using selective C–C bond cleavage to efficiently produce monomers in recycling processes. Furthermore, here we demonstrate a series of biologically sourced polymuconate polymers synthesized via simple free-radical polymerization that exhibit intrinsically weakened C–C bonds and controlled chemical recycling to monomers. Modifying the side chains and copolymerization ratios allows a wide range of mechanical property tuning, achieving performances comparable to those of commercial plastics such as polystyrene, polymethyl methacrylate and polybutadiene. Techno-economic analysis and life cycle assessment for production at a scale of 100 kilotons per year show that the materials are currently slightly more expensive and environmentally intensive compared with conventional rubbers. However, use of recycled materials via depolymerization can greatly decrease the cost and environmental impacts of polymuconate production (for example, down to US$1.59 per kilogram) to outperform its commercial counterparts.

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

Blending Compostable Plastics for Packaging Applications

Non-sustainable packaging materials (polymers) are a large portion of the increasing amount of plastic waste that become environmental pollutants. While many biodegradable or compostable polymers have been developed in recent years, most fail to compete with the non-sustainable polymers dominating the market, due to lack of certain desired properties, such as thermal (high melt temperature) and mechanical (high ductility) performance. For example, the popular compostable polymer polylactic acid (PLLA) has a high melt temperature but is very brittle. Another polymer, poly(d-valerolactone) (PVL) demonstrates great ductility but has a very low melt temperature. By blending PLLA and PVL, there is an opportunity to create a new biodegradable material with synergistic desired properties for packaging applications. In this study, we produce several (9) physical blends of PVL and PLLA with varying compositions of the two polymers while applying three different materials to make them more compatible (compatibilizers). We test the success of compatibilization by scanning electron microscopy (SEM), mechanic testing (strain at break) and differential scanning calorimetry (melting temperature). Overall, we highlight several promising materials with high compatibility and desired thermomechanical properties for sustainable packaging. Ideally, these materials could help mitigate future plastic pollution in Colorado and beyond.

blending↗
DOE OSTI2025

Repurposing Post-Consumer Polyethylene to Access Cross-Linked Polyethylene with Reprocessabilty, Recyclability, and Tunable Properties

Polyethylene (PE) is the most widely produced plastic but accumulation and resistance to degradation has significantly contributed to the plastic waste crisis. Upcycling has presented promising solutions to transform PE waste into value-added products. In this study, mixed post-consumer PE was successfully repurposed into reprocessable and chemically recyclable cross-linked polyethylene (XLPE). This process involved converting PE into telechelic oligomers, followed by repolymerization using a hybrid cross-linking system consisting of a dynamic cross-linker 2,4,6-triethoxy-1,3,5-triazine (TETA) and non-dynamic cross-linker tris(6-isocyanatohexyl)isocyanurate (Tri-HDI). In the resulting XLPE, TETA facilitated iterative reprocessing with minimal property degradation across cycles, whereas Tri-HDI helped preserve functional performance throughout service life. Compared to PE, XLPE exhibited enhanced mechanical properties, reduced creep deformation under application-relevant temperatures, and high temperature structural stability. Notably, copolymerizing PE oligomers with commercial macrodiols was employed to create composite XLPEs, enabling tuning material properties. After use, XLPE can be efficiently and selectively depolymerized under mild conditions, even when mixed with commercial insulator cables. This depolymerization allows for the recovery of the constituent building blocks, enabling purification and subsequent repolymerization for reuse. This approach demonstrates the potential of repurposing plastic waste into sustainable materials and fostering the development of a circular economy.

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMI↗