Search NASA⌕ Search

SEARCH · Search NASA

Results for “Synthetic polymers”

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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Miktoarm Star Polymers: Synthesis and Applications

Polymers with precisely controlled structure and function are in high demand across a diverse array of applications spanning the life sciences and nanotechnology. One prototypical example is a class of branched block copolymers known as miktoarm stars (μ-stars), which contain two or more arm compositions connected at a common junction. Miktoarm stars have attracted considerable attention since their physical properties can be different from conventional linear block copolymers. This perspective highlights the latest developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools used to avoid common preparation pitfalls and tailor properties for emerging applications. Furthermore, our contemporary perspective on μ-star polymers is a resource for inspiring future research into this exciting class of materials at the intersection of chemistry, physics, and advanced technology.

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

Developing nanometer scale, atomically precise metallo-catalysts with Molecular Lego

We propose to create atomically precise, highly robust, nanometer scale macromolecules that organize biomimetic metal binding groups in designed three-dimensional pockets to accelerate specific polymerization reactions. These atomically precise catalysts will create atomically precise polymers with improved mechanical and environmental properties from renewable building blocks. We seek to create and study nanometer scale catalysts that mimic metallo-enzymes in their activity and selectivity because these larger catalysts will be able to make more extensive non-covalent contacts with the transition state of the growing polymer. These catalysts will have extended lifetimes because they will better protect the metals and higher activity because additional reactive groups can be brought in close contact with the active site to enhance reactivity. They will be far more tolerant to extremes of temperature and will not denature in non-aqueous solvents because they are held together by multiple, strong, covalent bonds. Our approach to catalysts could be used to develop catalysts to replace noble metal-based catalysts when targeting other reactions, because the geometry of the active site enforced by the Molecular Lego scaffolding will access new reactivity, mimicking how nature uses earth abundant metals for much of its catalysis. We will initially target Lewis acid-based catalysts that assemble aliphatic polyesters with improved stereoselectivity, tacticity and complex alternation of monomers. Aliphatic polyesters have received growing attention as attractive, environmentally benign, and sustainable alternatives to polymers developed from petroleum feedstocks. Aliphatic polyesters are environmentally friendly because they undergo facile hydrolytic degradation to benign products, and they have excellent properties and high biocompatibility. We will assemble these catalysts using unique “Spiroligomers” (aka Molecular Lego) chemistry developed in the Schafmeister group combined with the organometallic chemistry expertise of the Dobereiner group. Polymers are an attractive synthetic target of nanoscale atomically precise catalysts because their resulting structure, stereochemistry and tacticity has profound impact on their properties (crystalline vs amorphous) and provides a readout of the catalytic mechanism. Polymer synthesis also serves as an example of “atomically precise manufacturing” where atomically precise nanoscale catalysts construct polymers with atomic precision at increasing length scales.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

The Synthesis and Ring-Opening Metathesis Polymerization of Energetic Norbornene Materials

Energetic norbornenes are promising candidates toward the development of new energetic polymers due to the synthetic versatility of norbornene ring-opening metathesis polymerizations used in commercial applications. We report the synthesis of two energetic norbornene materials that can be made in two steps with modest yields, containing either trinitroethanol or fluorodinitroethanol substituents. The norbornene monomers were then polymerized, and the polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), contact angle measurements, and proton and carbon nuclear magnetic resonance spectroscopies ( 1 H and 13 C{ 1 H} NMR). Additionally, small-scale safety data consisting of electrostatic discharge (ESD), friction (FS), and impact (IS) sensitivities were measured for the norbornene monomers and their resulting polymers. These analyses revealed that energetic norbornene materials are relatively insensitive and have densities comparable to that of TNT (1.47–1.81 g·cm –3 ).

36 MATERIALS SCIENCE↗
DOE OSTI2020

The impact of nanoparticle softness on its tracer diffusion coefficient in all polymer nanocomposites

The diffusion of nanoparticles in a polymer matrix is an area of current interest. However, a complete understanding is still limited as it is often difficult to quantify the much slower motion of nanoparticles in a polymer matrix. To combat this problem, we have developed a protocol to measure the diffusion coefficient of soft nanoparticles in a linear polymer matrix. Recently developed synthetic control over soft nanoparticle structures combined with this protocol provides a pathway to separately elucidate the effects of the molecular weight and nanoparticle softness on its diffusive behavior. These results indicate that the nanoparticle softness and deformability dictate its motion. Increasing the cross-linking density of the nanoparticle for all molecular weights increases its hardness and suppresses its motion in the linear matrix. Additionally, the nanoparticle molecular weight dependence deviates from the exponential dependence for star polymers suggesting that these nanoparticles benefit from the cooperative motion of the matrix to open pathways for the nanoparticle. Finally, comparison of these experimentally determined values to the Stokes–Einstein theory demonstrates that the nanoparticles diffuse much slower than a hard sphere. This is interpreted to indicate that there exist additional interactions between the nanoparticle and polymer matrix that are not captured by Stokes–Einstein, including threading or entanglement of the linear chain with the nanoparticle.

Rostom, Sahar↗
DOE OSTI2021

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells, and batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li + ). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li + partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium-metal batteries for electric mobility.

42 ENGINEERING↗
DOE OSTI2025

Bacterial-Retted Hemp Fiber/PLA Composites

The push for sustainability in all facets of manufacturing has led to an increased interest in biomass as an alternative to non-renewable materials. Hemp bast fiber mats were produced from a bacterial retting process, named BFM, as the fiber reinforcement. The objective of this study was to evaluate the feasibility of laminating BFM with polylactic acid (PLA) for a composite panel product. Since both BFM and PLA are biodegradable, the resulting BFM-PLA composites will be 100% biodegradable. PLA pallets were processed into thin polymer sheets which served as the matrix. The BFM and PLA plates were laminated in five layers and compression-molded into composite panels. Experiments were conducted on the three BFM-to-PLA ratios (35/65, 45/55, and 50/50). Mechanical properties (tensile and bending properties) and physical properties (thickness swell and water absorption) were tested and compared to the currently commercial sheet molding compound (SMC) from fiber glass. The thermal behavior of the BFM/PLA composites was characterized using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The developed BFM/PLA composite product is a sustainable alternative to existing synthetical fiber-reinforced polymer (FRP) that is biodegradable in landfill at the end of life.

Smith, Lee M. (ORCID:0000000264390357)↗
DOE OSTI2022

An Anthradithiophene Donor Polymer for Organic Solar Cells with a Good Balance between Efficiency and Synthetic Accessibility

Over the past few years, the organic photovoltaics technology (OPV) has reached remarkable power conversion efficiencies (PCEs), mostly thanks to the advent of nonfullerene acceptors as well as to a high level of materials engineering. Yet, the complex materials syntheses behind these results ultimately limit technological readiness. The quest for scalable organic compounds offering high PCE and reasonably low synthetic complexity is a must to close the gap between laboratory R&D and commercial products. The synthesis and full characterization of a new conjugated polymer called PATTD is reported herein, based on a novel anthradithiophene as an electron–rich building block coupled with a commercially available dithienylbenzodithiophenedione as an electron–withdrawing comonomer. Its photovoltaic properties are studied in blends with IT–4F and IDIC as acceptors. PATTD:IT–4F–based photovoltaic devices exhibit a PCE approaching 10% and over 2300 h shelf–life stability. Finally, the PATTD scalability factor (SF), together with the PATTD–based photovoltaic performances, lead to a PCE/SF value equal to 0.297, placing such devices into the innermost circle of OPV materials, achieving one of the best compromises between efficiency and synthetic complexity and at the same time offering promising industrial perspectives.

14 SOLAR ENERGY↗
DOE OSTI2022

Modular Approach for the Synthesis of Bottlebrush Diblock Copolymers from Poly(Glycidyl Methacrylate)-block-Poly(Vinyldimethylazlactone) Backbones

A strategy that enables the facile synthesis of bottlebrush block copolymers with flexible backbones was developed. A demonstration of the strategy’s utility was carried out by grafting end-functionalized polymethylmethacrylate (PMMA) and polystyrene (PS) to the dually reactive block copolymer, poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone) (PGMA-b-PVDMA). Five different bottlebrush diblock copolymers were investigated by size-exclusion chromatography (SEC), 1H NMR, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray scattering methods, atomic force microscopy (AFM), rheology and computational simulations using molecular dynamics (MD), and self-consistent field theory (SCFT). A relationship between the glass transition temperature and the fraction of chain ends was demonstrated by DSC and highlights the potential of this synthetic method to tailor polymer properties. All five samples were found to be in a disordered phase exhibiting multiscale structures revealed by two broad peaks in small-angle X-ray scattering (SAXS) that can be attributed to graft-to-graft and backbone-to-backbone density correlations using MD simulations. The SCFT-based simulations justify the observation of a disordered phase due to its stabilization by the grafts. Additionally, this modular approach can be easily extended to other grafts, including responsive, conducting, and charged polymers with the prerequisite end groups. The versatility and ease of assembling these functional bottlebrushes constitute a powerful “toolbox” method for the rapid and scalable synthesis of novel bottlebrush block copolymers with desired properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Polymer connectivity governs electrophotocatalytic activity in the solid state

The reductive functionalization of inert substrates such as chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging strategy to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is limited by poor stability and mechanistic ambiguity. Here, in this work, we demonstrate heterogeneous electrophotocatalysis using redox-active rylene diimide polymers for the reduction of chloroarenes. We find that the electrophotocatalytic activity varies dramatically as a function of the rylene diimide and the redox-inactive polymer backbone. In particular, a flexible, non-conjugated perylenediimide polymer outperforms all other tested electrophotocatalysts. Transient absorption spectroscopy reveals that precomplexation between the doubly reduced perylenediimide and the haloarene substrate is key to productive catalysis. Overall, this work highlights heterogeneous electrophotocatalysis using insoluble redox-active organic materials and provides critical structure–property insights into solid-state electrophotocatalytic activity, informing the development of next-generation materials for sustainable synthesis.

electrocatalysis↗
DOE OSTI2024

Abstract for CRADA between National Energy Technology Laboratory and American Institute of Chemical Engineers dba RAPID Manufacturing Institute

NETL and RAPID Manufacturing will develop advanced electromagnetic (EM) reactors and catalysts to produce light olefins from alternative feedstocks using CO2 soft oxidation. Light olefins are the building blocks for many plastic products, in addition to synthetic fibers, rubbers, and polymers. This project has the potential to produce high-value light olefins from alternative feedstocks with reduced energy consumption (50-70%), carbon intensity (50-70%), and production cost (15-25%) compared to the traditional olefin production processes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Gold Catalyzed Polymerization Reactions of Unsaturated Substrates: Towards New Functional, Recyclable, and Upcycled Aromatic Polymers (Final Report)

The overarching goal of this project lied in the translation of gold (Au) catalyzed small molecule synthetic transformations to the field of polymer science, the generation of new macromolecular structures, and the application of the materials and methodologies produced toward sustainable polymer development and chemical upcycling. Specifically, this project aimed to polymerize monomers based on unsaturated precursors and access novel polymeric materials through the extension of Au catalyzed intermolecular processes. The specific objectives of this project comprised: (1) the extension of Au-catalyzed intermolecular reactions to bifunctional monomers and the polycondensation of diverse nucleophiles; (2) to gain fundamental mechanistic insight into Au-catalyzed polymerizations; (3) the application of these reactions to the synthesis of new classes of aromatic polymers that can be readily and/or selectively deconstructed; and (4) to apply these chemistries to post-polymerization modification (PPM) of commercially relevant polyaromatic substrates, including post-industrial plastics and post-consumer waste.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Spin Glass Behavior and Giant Magnetoresistance via Aliovalent Fe/Ni Alloying in Amorphous Tetrathiafulvalene-Tetrathiolate Coordination Polymers

The discovery of materials with programmable combinations of charge transport and magnetic properties is a major goal in synthetic chemistry. Molecular materials, such as coordination polymers (CPs), are emerging candidates in this field due to their synthetic modularity. While there are many conductive or magnetic CPs, single-component examples with both properties are still emerging. Here, in this work, we demonstrate how alloying paramagnetic Fe(III) centers into a highly conductive Ni-based CP results in novel amorphous materials with high conductivity and giant magnetoresistance. Aliovalent doping with paramagnetic Fe centers engenders spin-glass transitions, while Ni and the strong π-stacking interactions of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFtt) ligands support conductivity. Ni 0.69 Fe 0.31 TTFtt has σ ≈ 200 S/cm and a 1.8 K magnetoresistance of −52% at 5 T, among the largest for any coordination solid. This work demonstrates not only how magnetic properties can be rationally incorporated into conductive CPs, but also an unexpected potential for amorphous materials in spintronic applications.

amorphous materials↗
DOE OSTI2021

Protein-Mimetic Self-Assembly with Synthetic Macromolecules

Protein-mimetic amphiphiles have significant promise as a platform to access the complex functions of natural biological materials and incorporate the tunability and environmental resilience of synthetic materials. The fields of polymer chemistry and chemical biology have concurrently approached the development of biomimetic amphiphiles with materials ranging from random amphiphilic copolymers to peptide–lipid conjugates. In this Perspective, we incorporate strategies from diverse chemical arenas for controlling assembled morphologies and dynamics of protein-mimetic synthetic macromolecules. An overview of significant advances in peptide amphiphiles and single-chain polymer nanoparticles provides the foundation for comparing recent advances in the implementation of multiple intermolecular interactions and computational strategies to fine-tune the assembled structures. We aim to bridge these fields, combining insights from multiple disciplines to inspire new approaches for the development of protein-mimetic materials, as these assemblies have far-reaching applications including in the development of new sensors, catalysts, and therapeutics.

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

Tunable, biodegradable grafting-from glycopolypeptide bottlebrush polymers

The cellular glycocalyx and extracellular matrix are rich in glycoproteins and proteoglycans that play essential physical and biochemical roles in all life. Synthetic mimics of these natural bottlebrush polymers have wide applications in biomedicine, yet preparation has been challenged by their high grafting and glycosylation densities. Using one-pot dual-catalysis polymerization of glycan-bearing α-amino acid N-carboxyanhydrides, we report grafting-from glycopolypeptide brushes. The materials are chemically and conformationally tunable where backbone and sidechain lengths were precisely altered, grafting density modulated up to 100%, and glycan density and identity tuned by monomer feed ratios. The glycobrushes are composed entirely of sugars and amino acids, are non-toxic to cells, and are degradable by natural proteases. Inspired by native lipid-anchored proteoglycans, cholesterol-modified glycobrushes were displayed on the surface of live human cells. Our materials overcome long-standing challenges in glycobrush polymer synthesis and offer new opportunities to examine glycan presentation and multivalency from chemically defined scaffolds.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin

Lignin may serve as a renewable feedstock for the production of chemicals and fuels if mild, scalable processes for its depolymerization can be devised. The use of small organic thiols represents a bioinspired strategy to cleave the β–O–4 bond, the most common linkage in lignin. In the present study, synthetic β–O–4 linked polymers were treated with organic thiols, yielding up to 90 % cleaved monomer products. Lignin extracted from poplar was also treated with organic thiols resulting in molecular weight reductions as high as 65 % (Mn) in oxidized lignin. Thiol–based cleavage of other lignin linkages was also explored in small–molecule model systems to uncover additional potential pathways by which thiols might depolymerize lignin. The success of thiol–mediated cleavage on model dimers, polymers, and biomass–derived lignin illustrates the potential utility of small redox–active molecules to penetrate complex polymer matrices for depolymerization and subsequent valorization of lignin into fuels and chemicals.

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

Highly tunable structure-by-design polymer brush membranes for organic solvent nanofiltration

Synthetic polymeric nanofiltration membrane processes offer an alternate low-energy option to energy-intensive distillation to fractionate similar size organic solvents for chemical, petroleum, food and biotechnology industries. Here, in this study, we synthesize and test a new class of structure-by-design hydrophilic polymeric brush membranes, that address the limitations of commercial polymer membranes, are tunable and exhibit commercially relevant filtration performance. Because these brush membranes are grafted by Single Electron Transfer-Living Radical Polymerization (SET-LRP) and replace statistically random phase inversion or interfacial polymerization used for synthesizing commercial polymer membranes, their porous structure can be remodeled by varying their morphology and chemistry. We graft hydroxyethyl methacrylate (HEMA) brush structures with short and long crosslinkers, demonstrate two competing phenomena - pore stiffening and opening - and obtain high selectivity at reasonable permeability for commercially relevant methanol/toluene separation. This new class of stable, tunable, and scalable membranes offers exciting opportunities to reduce energy for separation of organic solvents.

42 ENGINEERING↗
DOE OSTI2022

Synthetic Nuances to Maximize n-Type Organic Electrochemical Transistor and Thermoelectric Performance in Fused Lactam Polymers

A series of fully fused n-type mixed conduction lactam polymers p(g 7 NC n N), systematically increasing the alkyl side chain content, are synthesized via an inexpensive, nontoxic, precious-metal-free aldol polycondensation. Employing these polymers as channel materials in organic electrochemical transistors (OECTs) affords state-of-the-art n-type performance with p(g 7 NC 10 N) recording an OECT electron mobility of 1.20 x 10 -2 cm 2 V -1 s -1 and a μC* figure of merit of 1.83 F cm -1 V -1 s -1. In parallel to high OECT performance, upon solution doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine (N-DMBI), the highest thermoelectric performance is observed for p(g 7 NC 4 N), with a maximum electrical conductivity of 7.67 S cm -1 and a power factor of 10.4 μWm -1 K -2 . These results are among the highest reported for n-type polymers. Importantly, while this series of fused polylactam organic mixed ionic-electronic conductors (OMIECs) highlights that synthetic molecular design strategies to bolster OECT performance can be translated to also achieve high organic thermoelectric (OTE) performance, a nuanced synthetic approach must be used to optimize performance. Herein, we outline the performance metrics and provide new insights into the molecular design guidelines for the next generation of high-performance n-type materials for mixed conduction applications, presenting for the first time the results of a single polymer series within both OECT and OTE applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗