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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Feasibility of Recovering and Recycling Polymer Composites from End-of-Life Marine Renewable Energy Structures: A Review

Over the last few decades, several marine renewable energy (MRE) technologies, such as wave energy converters (WECs) and current energy converters (CECs), have been developed. As opposed to traditional materials such as metal alloys, the structure of these technologies is made up of polymer and polymer composite materials. Most structures have been made using thermoset polymer composites; however, since thermoset polymer composites are not recyclable and lack sustainability, and with recent innovations in recyclable resins, bio-based resins, and the development of additive manufacturing technologies, thermoplastic polymers are increasingly being used. Nevertheless, the methodologies for identifying end-of-life options and recovering these polymer composites, as well as the recycling and reuse processes for MRE structures, are not well-studied. Specifically, since these MRE structures are subjected to salinity, moisture, varying temperature, biofouling, and corrosion effects depending on their usage, the recyclability after seawater aging and degradation needs to be explored. Hence, this review provides an in-depth review of polymer composites used in marine applications, the hygrothermal aging studies conducted so far to understand the degradation of these materials, and the reuse and recycling methodologies for end-of-life MRE structures, with a particular emphasis on sustainability.

16 TIDAL AND WAVE POWER↗
DOE OSTI2022

Influence of Thermal Treatment on Preceramic Polymer Grafted Nanoparticle Network Formation: Implications for Thermal Protection Systems and Aerospace Propulsion Components

Preceramic polymer grafted nanoparticles (PCP GNPs) offer potential advantages in the production of polymer-derived ceramic composites compared to neat preceramic polymers (PCPs), such as reduced thermal shrinkage and increased char yield. In comparison to traditional composites (particles + free polymer), PCPs avoid issues of compatibility, agglomeration, and phase separation during processing and provide routes to control nanoparticle arrangement. Prior literature has established that the conversion efficiency of PCPs and PCP GNPs to ceramics and ceramic composites is linked to the thermal pretreatment of these precursor polymers (e.g., curing). In this paper, we investigate the material transformations that occur when exposing PCP GNPs to a low-temperature thermal treatment (≤250 °C) prior to pyrolysis. The PCP GNPs explored in this study possessed silica nanoparticle cores but were distinct in their PCP coronas, having poly(1,1-dimethylpropylsilane) (allyl-GNP)- or poly(1,1-dimethylbenzylethylsilane) (styryl-GNP)-grafted polymers. After undergoing low-temperature thermal treatment, these PCP GNPs exhibited increased char yield at 800 °C; however, unlike commercial PCPs (e.g., allylhydridopolycarbosilane (SMP-10)), obvious cross-linkable sites are not present in the PCP corona structure. Differential scanning calorimetry, oscillatory rheology, and X-ray photon correlation spectroscopy were utilized to elucidate the thermally induced material changes in the allyl- and styryl-GNPs. Thermally induced changes to the structure and behavior of the PCP GNPs were determined to be linked to the chemical structure of the grafted polycarbosilane chains. Styryl-GNPs experienced a curing event between 180 and 250 °C, effecting the formation of a network, which contributed to char yield improvement (at 800 °C). The nanoscale dynamics of this material also shows a transition from diffuse behavior to ballistic behavior because of the cross-linking event. Conversely, the allyl-GNPs did not exhibit a curing event under heat treatment but did show an increase in thermally induced physical cross-linking. The allyl-GNP physical network is stronger after the first cycle of thermal treatment, and it is considered that this contributed to the improvement in char yield post thermal treatment. The advancements in the understanding of the cross-linking behavior of these hybrid materials are expected to advance the application of these materials to turbine engine, advanced friction, and heat-shielding components.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Degradable Polymer Stars Based on Tannic Acid Cores by ATRP

Degradable polymers are crucial in order to reduce plastic environmental pollution and waste accumulation. In this paper, a natural product, tannic acid was modified to be used as a polymer star core. The tannic acid was modified with atom transfer radical polymerization (ATRP) initiators and characterized by 1H NMR, FT-IR, and XPS. Twenty-five arm polymer stars were prepared by photoinduced ATRP of poly(methyl methacrylate) (PMMA) or poly(oligo(ethylene oxide) methacrylate) (molar mass Mw = 300 g/mol) (P(OEO300MA)). The polymer stars were degraded by cleaving the polymer star arms attached to the core by phenolic esters under mild basic conditions. The stars were analyzed before and after degradation by gel permeation chromatography (GPC). Cytotoxicity assays were performed on the P(OEO300MA) stars and corresponding degraded polymers, and were found to be nontoxic at the concentrations tested.

36 MATERIALS SCIENCE↗
DOE OSTI2017

The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F 4 TCNQ‐Doped Conjugated Polymer Films

Abstract The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F 4 TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F 4 TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F 4 TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm 2 V −1 s −1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.

Scholes, D. Tyler↗
DOE OSTI2023

Enhanced Optical Contrast and Switching in Near‐Infrared Electrochromic Devices by Optimizing Conjugated Polymer Oligo(Ethylene Glycol) Sidechain Content and Gel Electrolyte Composition

Abstract A detailed investigation addressing the effects of functionalizing conjugated polymers with oligo(ethylene glycol) (EG n ) sidechains on the performance and polymer‐electrolyte compatibility of electrochromic devices (ECDs) is reported. The electrochemistry for a series of donor‐acceptor copolymers having near‐infrared (NIR)‐optical absorption, where the donor fragment is 3,4‐ethylenedioxythiophene (EDOT) or an EG n functionalized bithiophene (g2T) and the acceptor fragment is diketopyrrolopyrrole (DPP) functionalized with branched alkyl or EG n sidechains, is extensively probed. ECDs are next fabricated and it is found that EG n sidechain incorporation must be finely balanced to promote polymer‐electrolyte compatibility and provide efficient ion exchange. Proper electrolyte‐cation pairing and polymer structural tuning affords a 2x increase in optical contrast (from 12% to 24%) and >60x reduction in switching time (from 20 to 0.3 s). Atomic force microscopy (AFM)/grazing incidence wide‐angle X‐ray scattering (GIWAXS) characterization of the polymer film morphology/microstructure reveals that an over‐abundance of EG n sidechains generates large polymer crystallites, which can suppress ion exchange. Lastly, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) indicates sidechain/electrolyte identity does not influence the electrolyte penetration depth into the films, and EG n sidechain inclusion increases electrolyte cation uptake. The material structural design insight and guidelines regarding the polymer‐electrolyte ion insertion/expulsion dynamics reported here should be of significant utility for developing next‐generation mixed ionic‐electronic conducting materials.

Chemistry↗
DOE OSTI2019

Conjugated Carbon Cyclic Nanorings as Additives for Intrinsically Stretchable Semiconducting Polymers

Abstract Molecular additives are often used to enhance dynamic motion of polymeric chains, which subsequently alter the functional and physical properties of polymers. However, controlling the chain dynamics of semiconducting polymer thin films and understanding the fundamental mechanisms of such changes is a new area of research. Here, cycloparaphenylenes (CPPs) are used as conjugated molecular additives to tune the dynamic behaviors of diketopyrrolopyrrole‐based (DPP‐based) semiconducting polymers. It is observed that the addition of CPPs results in significant improvement in the stretchability of the DPP‐based polymers without adversely affecting their mobility, which arises from the enhanced polymer dynamic motion and reduced long‐range crystalline order. The polymer films retain their fiber‐like morphology and short‐range ordered aggregates, which leads to high mobility. Fully stretchable transistors are subsequently fabricated using CPP/semiconductor composites as active layers. These composites are observed to maintain high mobilities when strained and after repeated applied strains. Interestingly, CPPs are also observed to improve the contact resistance and charge transport of the fully stretchable transistors. ln summary, these results collectively indicate that controlling the dynamic motion of polymer semiconductors is proved to be an effective way to improve their stretchability.

Mun, Jaewan↗
DOE OSTI2020

3,4‐Dicyanothiophene—a Versatile Building Block for Efficient Nonfullerene Polymer Solar Cells

Abstract In this contribution, a versatile building block, 3,4‐dicyanothiophene (DCT), which possesses structural simplicity and synthetic accessibility for constructing high‐performance, low‐cost, wide‐bandgap conjugated polymers for use as donors in polymer solar cells (PSCs), is reported. A prototype polymer, PB3TCN‐C66, and its cyano‐free analogue polymer PB3T‐C66, are synthesized to evaluate the potential of using DCT in nonfullerene PSCs. A stronger aggregation property in solution, higher thermal transition temperatures with higher enthalpies, a larger dipole moment, higher relative dielectric constant, and more linear conformation are exhibited by PB3TCN‐C66. Solar cells employing IT‐4F as the electron acceptor offer power conversion efficiencies (PCEs) of 11.2% and 2.3% for PB3TCN‐C66 and PB3T‐C66, respectively. Morphological characterizations reveal that the PB3TCN‐C66:IT‐4F blend exhibits better π–π paracrystallinity, a contracted domain size, and higher phase purity, consistent with its higher molecular interaction parameter, derived from thermodynamic calculations. Moreover, PB3TCN‐C66 offers a higher open‐circuit voltage and reduced energy loss than most state‐of‐the‐art wide‐bandgap polymers, without the need of additional electron‐withdrawing substituents. Two additional polymers derived from DCT also demonstrate promising performance with a higher PCE of 13.4% being achieved. Thus, DCT represents a versatile and promising building block for constructing high‐performance, low‐cost, conjugated polymers for application in PSCs.

Zhang, Bo↗
DOE OSTI2026

Selective Electrochemical End‐Group Removal Enhances Polymer Thermal Stability

Here we introduce an electrochemical strategy for the selective and quantitative removal of thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) or photoiniferter polymerization. Our results indicate that applying a cathodic potential in an undivided cell promotes reductive cleavage of the thiocarbonylthio moiety, generating terminal polymer radicals that are efficiently capped with hydrogen atoms in the presence of benign donors. This transformation proceeds cleanly across diverse polymer backbones and end-group chemistries, including trithiocarbonates and dithiobenzoates, without chain coupling or degradation. Moreover, the applied potential can be tuned to enable chemoselective end-group removal in mixed-polymer systems, a level of control inaccessible by thermal, photochemical, or nucleophilic strategies. Beyond delivering colorless and optically transparent materials, electrochemical end-group removal significantly enhances polymer stability. Poly(methyl methacrylate) subjected to electrochemical end-group removal exhibited a T 95 of 342 °C, exceeding the stabilities of analogous polymers with end groups removed by aminolysis (T 95 = 260 °C) or radical-based methods (T 95 = 299 °C). These findings demonstrate redox-directed post-polymerization modification as a tool for designing robust, transparent, and thermally stable macromolecules and establish electrochemistry as a platform strategy in polymer synthesis and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Ending Aging in Super Glassy Polymer Membranes

Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N-2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

Lau, CH↗
DOE OSTI2015

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-range depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion

36 MATERIALS SCIENCE↗
DOE OSTI2020

Engineering Supramolecular Polymer Conformation for Efficient Carbon Nanotube Sorting

Supramolecular polymer sorting is a promising approach to separating single-walled carbon nanotubes (CNTs) by electronic type. Unlike conjugated polymers, they can be easily removed from the CNTs after sorting by breaking the supramolecular bonds, allowing for isolation of electronically pristine CNTs as well as facile recycling of the sorting polymer. However, little is understood about how supramolecular polymer properties affect CNT sorting. Herein, chain stoppers are used to engineer the conformation of a supramolecular sorting polymer, thereby elucidating the relationship between sorting efficacy and polymer conformation. Through NMR and UV–vis spectroscopy, small-angle X-ray scattering (SAXS), and thermodynamic modeling, it is shown that this supramolecular polymer exhibits ring–chain equilibrium, and that this equilibrium can be skewed toward chains by the addition of chain stoppers. Furthermore, by controlling the stopper–monomer ratio, the sorting yield can be doubled from 7% to 14% without compromising the semiconducting purity (>99%) or properties of sorted CNTs.

42 ENGINEERING↗
DOE OSTI2018

Preparation and Characterization of New Environmental Functional Polymers Based on Vanillin and N-isopropylacrylamide for Post Polymerization

The study aims to synthetize a new functional acrylate monomer from vanillin in one step reaction. The new monomer has called by vanillin acrylate and abbreviated (VA). It was confirmed by chemical methods 1H NMR, 13C, IR and UV indicated logic results. The homopolymer has been prepared by free radical polymerization and characterized chemically and physically, the {sup 1}HNMR and IR have proofed the presence of aldehyde group in the polymer main chain. This monomer was used to synthesize three different molar concentrations of temperature responsive functional polymers with N-isopropylacrylamide via free radical polymerization by AIBN in solution. The {sup 1}H NMR was used for determination of actual mole concentration of each monomer. The aldehyde group in polymers were used as a linker for grafting with primary amine compounds by click reactions to form Schiff’s base imine compounds. The grafted copolymers were also investigated by 1H NMR and IR for structure elucidation. Gel permeation chromatography GPC was used for determination the molecular weight and polydispersity; DSC for glass temperature of solid polymers; XRD for crystallinity. UV–Vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution before and after grafting, not only in deionized water but in pH 5 and pH 11. Graphical Abstract: Synthesis of new functional monomer based on vanillin in one step reaction. Monomer has been successfully polymerized by free radical polymerization using AIBN as initiator. Three different mole ratios (10, 15, 20 mol%) of copolymer with NIPAAm were prepared. All monomers and polymers have been chemically elucidated. The aldehyde functional group used as linker for primary amine compounds, the final products have been characteristics as T, pH dual responsive polymers the phase transition temperature of copolymer before and after grafting was determined by UV.vis Spectroscopy. .

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

Rheological Behaviour, Mechanical Properties and Processability of Biodegradable Polymer Systems for Film Blowing

Films for agricultural or packaging applications are typically made of low density polyethylene (LDPE). They are produced through the film blowing process, which requires the use of polymers with suitable rheological properties. Furthermore, the short shelf-life which is often related to many packed products leads to huge amounts of plastic-based wastes. This suggests the use of biodegradable and/or compostable polymers in replacement for traditional ones. To this regard, only few data exist on the rheological properties of biodegradable polymers undergoing film blowing processing. In this work, a detailed investigation on the rheological, mechanical and processability behaviour of some biodegradable polymers (originating from MaterBi{sup ®} and Bioflex{sup ®} commercial groups) was carried out, in order to assess their suitability to industrial-scale film blowing by direct comparison with a traditional non-biodegradable polymer (LDPE). Rheological tests under shear and non-isothermal elongational flow allowed to find out the two most suitable polymer grades. The film blowing production operations at different draw and blow-up ratios (from 2.5 to 3.5) showed that the two samples are suitable for industrial scale operations. Results from tensile and impact tests indicated that the two selected polymers exhibit significantly different mechanical properties (up to 10–15%).

36 MATERIALS SCIENCE↗
DOE OSTI2018

Radical Degradation Processes Initiated by Catalytic Nanoparticles of CoFe{sub 2}O{sub 4} Towards Polymer Waste Application

Polymer waste presents a modern environmental challenge due to the long-term stability of these materials. Elastomer-based polymers (e.g., tires, pipelines and shoes) are unique in comprising numerous double bonds, which are typically sensitive to radical-initiated oxidative degradation leading to the scission of polymer chains. In this paper, we propose a new approach for radical-initiated oxidative degradation of polymers using cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles (NPs). We show that magnetic CoFe{sub 2}O{sub 4} NPs can effectively catalyze the oxidative degradation of polybutadiene (PB), offering easy magnetic recycling and reuse without affecting their catalytic efficiency. The CoFe{sub 2}O{sub 4} NPs were synthesized via a facile surfactant-free method based on a sonochemical reaction. We used methyl ethyl ketone peroxide (MEKP), a model system, to study the rate of radical decomposition catalyzed by the NPs. The radical decomposition rates were determined by following the discoloration of methylene blue (MB) using ultraviolet–visible (UV/Vis) spectroscopy; electron paramagnetic resonance (EPR) measurements were used to study radical formation. The radical-initiated oxidative degradation of PB was studied by thermogravimetric analysis with mass spectrometry detection (TGA–MS). Our results show that cobalt ferrite NPs lead to formation of polymers with low molecular weight fragments and crosslinking, indicating that these NPs are very effective catalysts for the radical degradation of PB. CoFe{sub 2}O{sub 4} NPs are potentially suitable for other polymers, hence this approach may provide a novel route for the chemical (tertiary) recycling of polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Self-Repairing Polymer-Modified Cements for High Temperature Geothermal and Fossil Energy Applications

In this work five novel polymer-cement composite formulations were prepared and evaluated as potential cementitious material alternatives to conventional wellbore cement. These cement composites were cured at 200 °C and their mechanical properties, including compressive strength, Young modulus, shear bond strength to steel casing, and self-healing and re-adhering (to steel) capability. Thermal stability was also evaluated by curing these cement materials at 200 °C for up to one month followed by determining their mineralogy and chemical composition by X-ray diffraction spectroscopy, 13C NMR, and total organic carbon. Permeability analysis was performed before and after healing a longitudinal fracture on unmodified cements and polymer-cement composites with the later showing lower (2nd/1st) permeability ratios with respect to base cements. Furthermore, a reduction in permeability of up to 80X on average with respect to their unmodified (base) cement, was observed in two polymer-cement formulations suggesting that the introduction of these polymers bring about self-healing capability. Two of the best performing polymer-cement composites were exposed to 30-day curing period at 200 °C showing that their self-healing capability is maintained. The composite stability is associated to the fact that the polymer material is stable as demonstrated by total organic carbon and NMR spectroscopy. These advanced polymer-cement composites with higher ductility and self-healing capability could be used as alternative wellbore cement materials for geothermal and fossil energy applications.

Rod, Kenton A.↗
DOE OSTI2021

Damage evolution in polymer due to exposure to high-pressure hydrogen gas

The use of hydrogen as a fuel is increasing exponentially, and the most economical way to store and transport hydrogen for fuel use is as a high-pressure gas. Polymers are widely used for hydrogen distribution and storage systems because they are chemically inert towards hydrogen. However, when exposed to high-pressure hydrogen, some hydrogen diffuses through polymers and occupies the preexisting cavities inside the material. Upon depressurization, the hydrogen trapped inside polymer cavities can cause blistering or cracking by expanding these cavities. A continuum mechanics--based deformation model was deployed to predict the stress distribution and damage propagation while the polymer undergoes depressurization after high-pressure hydrogen exposure. The effects of cavity size, cavity location, and pressure inside the cavity on damage initiation and evolution inside the polymer were studied. The stress and damage evolution in the presence of multiple cavities was also studied, because interaction among cavities alters the damage and stress field. It was found that all these factors significantly change the stress state in the polymer, resulting in different paths for damage propagation. The effect of adding carbon black filler particles and plasticizer on the damage was also studied. It was found that damage tolerance of the polymer increases drastically with the addition of carbon black fillers, but decreases with the addition of the plasticizer.

Kulkarni, Shank S.↗
DOE OSTI2017

Polymer assisted growth of high-quality perovskite films by Lewis acid-base adduct for efficient planar-heterojunction solar cells

Highlights: • Polymer assisted growth of high-quality perovskite films was demonstrated. • Polymer PMMA can retard nucleation and crystal growth of perovskite. • The interaction between the perovskite films and PMMA was addressed. • Planar-heterojunction solar cells with efficiencies of 15% were achieved. - Abstract: Long-chain insulating polymers dissolved in perovskite precursor solution can assemble the polymer scaffold acted as the function of TiO{sub 2} porous layer to improve the quality of the perovskite films. Here, perovskite films with high electronic quality were prepared by mediating nucleation and crystal growth. Polymer post treatment can induce Lewis acid-base reaction with PbCl{sub 2}, which alleviates the reaction velocity between PbCl{sub 2} and CH{sub 3}NH{sub 3}I, and then retard perovskite crystallization. The interactions between the perovskite films and polymer with different concentration are addressed to interpret the function and evolution of the polymer long-chains during the annealing process. These solar cells exhibit efficiency more than 15% with small variation. Our work demonstrates the value of retarding nucleation and crystal growth by Lewis acid-base adducts for high-quality perovskite films.

36 MATERIALS SCIENCE↗