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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Controlled patterning of crystalline domains by frontal polymerization

Materials with hierarchical architectures that combine soft and hard material domains with coalesced interfaces possess superior properties compared with their homogeneous counterparts. These architectures in synthetic materials have been achieved through deterministic manufacturing strategies such as 3D printing, which require an a priori design and active intervention throughout the process to achieve architectures spanning multiple length scales. Here we harness frontal polymerization spin mode dynamics to autonomously fabricate patterned crystalline domains in poly(cyclooctadiene) with multiscale organization. This rapid, dissipative processing method leads to the formation of amorphous and semi-crystalline domains emerging from the internal interfaces generated between the solid polymer and the propagating cure front. The size, spacing and arrangement of the domains are controlled by the interplay between the reaction kinetics, thermochemistry and boundary conditions. Small perturbations in the fabrication conditions reproducibly lead to remarkable changes in the patterned microstructure and the resulting strength, elastic modulus and toughness of the polymer. Furthermore, this ability to control mechanical properties and performance solely through the initial conditions and the mode of front propagation represents a marked advancement in the design and manufacturing of advanced multiscale materials. Drawing inspiration from biological systems in which structural complexity develops through dissipative reaction–diffusion processes, this study explores a transformative synthetic manufacturing strategy aimed at harnessing the principles underpinning morphogenic growth, unlocking new avenues for advanced materials design and fabrication. Synthetic coupled reaction-transport processes offer a versatile yet relatively underexplored method to manipulate the spatial attributes of synthetic materials10. Here we introduce an innovative manufacturing approach based on frontal ring-opening metathesis polymerization (FROMP) that draws parallels with morphogenic growth and development, enabling the formation of patterned microstructures within polymeric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Prediction of an alternative high-pressure route to polymeric carbon dioxide as a metastable energetic material

The use of pressure to obtain new materials that can be recovered under ambient conditions is a central problem in high-pressure physics. Despite decades of research, this goal has only been achieved in the laboratory for a few notable examples, such as diamond and cubic boron nitride. An area of significant interest is the transformation under compression of light-element molecular compounds to extended covalent-bonded (polymeric) solids. Among them, CO 2 has been extensively studied because of its status as a prototypical simple molecular system with a rich phase diagram and due to its fundamental role in Earth’s physics and chemistry. One of its polymeric crystalline phases, accessible at extreme pressures and temperatures, has been recently quenched to ambient pressure, but below room temperature. Here we report ab initio calculations predicting that isothermal compression of a carbon monoxide and oxygen mixture (CO+O 2 ), rather than the compound CO 2 , lowers the onset of C-polymerization at room temperature from ~ 118 GPa to ~ 7 GPa (complete by ~ 23 GPa). Moreover, it leads to the formation of an intrinsically different polymer with enhanced metastability. We predict that this dense phase is an energetic material which can potentially be recovered to ambient pressure and temperature.

Paul, Reetam [Lawrence Livermore National Laborato↗
DOE OSTI2020

Mg 2+ ion-catalyzed polymerization of 1,3-dioxolane in battery electrolytes

Electrolyte salts with Mg 2+ and Al 3+ Lewis acidic cations demonstrate polymerization of 1,3-dioxolane. The speed and extent of the reaction depends on coordination of the anion with the Mg 2+ cation catalyst. Weakly coordinating anions such as TFSI - aid faster polymerization while strongly coordinating anions such as ClO 4 - hinder the polymerization.

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

Metal–organic framework (MOF) materials as polymerization catalysts: a review and recent advances

Synthetic polymers are ubiquitous across both the industrial and consumer segments of the world economy. Catalysts enable rapid, efficient, selective, and even stereoselective, formation of desired polymers from any of a host of candidate monomers. While numerous molecular catalysts have been shown to be effective for these reactions, separation of the catalysts from reaction products is typically difficult – a potentially problematic complication that suggests instead the use of heterogeneous catalysts. Many of the most effective heterogeneous catalysts, however, comprise supported collections of reaction centres that are decidedly nonuniform in their composition, siting, and activity. Nonuniformity complicates atomic-scale evaluation of the basis for catalytic activity and thus impedes scientific hypothesis-driven understanding and development of superior catalysts. In view of the fundamental desirability of structural and chemical uniformity at the meso, nano, and even atomic scale, crystallographically well-defined, high-porosity metal–organic frameworks (MOFs) have attracted attention as model catalysts and/or catalyst-supports for a wide variety of chemical transformations. In the realm of synthetic polymers, catalyst-functionalized MOFs have been studied for reactions ranging from coordination-mediated polymerization of ethylene to visible-light initiated radical polymerizations. Nevertheless, many polymerization reactions remain to be explored – and, no doubt, will be explored, given the remarkable structural and compositional diversity of attainable MOFs. Noteworthy emerging studies include work directed toward more sophisticated catalytic schemes such as polymer templating using MOF pore architectures and tandem copolymerizations using MOF-supported reaction centres. Finally, it is appropriate to recognize that MOFs themselves are synthetic polymers – albeit, uncoventional ones.

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

Post-polymerization modification of polymethacrylates enabled by keto–enol tautomerization

We report a post-polymerization modification strategy to functionalize methacrylic copolymers through enol-ester transesterification. A new monomer, vinyl methacryloxy acetate (VMAc), containing both enol-ester and methacryloyl functionality, was successfully copolymerized with methyl methacrylate (MMA) by selective reversible addition–fragmentation chain transfer (RAFT) polymerization. Post-polymerization modification of pendent enol esters proceeded through an “irreversible” transesterification process, driven by the low nucleophilicity of the tautomerization product, to result in high conversion under mild conditions.

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

Swelling characteristics of DNA polymerization gels

The development of biomolecular stimuli-responsive hydrogels is important for biomimetic structures, soft robots, tissue engineering, and drug delivery. DNA polymerization gels are a new class of soft materials composed of polymer gel backbones with DNA duplex crosslinks that can be swollen by sequential strand displacement using hairpin-shaped DNA strands. The extensive swelling can be tuned using physical parameters such as salt concentration and biomolecule design. Previously, DNA polymerization gels have been used to create shape-changing gel automata with a large design space and high programmability. Here we systematically investigate how the swelling response of DNA polymerization gels can be tuned by adjusting the design and concentration of DNA crosslinks in the hydrogels or DNA hairpin triggers, and the ionic strength of the solution in which swelling takes place. Finally, we also explore the effect hydrogel size and shape have on the swelling response. Tuning these variables can alter the swelling rate and extent across a broad range and provide a quantitative connection between biochemical reactions and macroscopic material behaviour.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Organo-catalyzed deamination of polystyrene sulfonamide for diverse post-polymerization modification of styrenic polymers

Post-polymerization modification allows for the incorporation of functional groups that would otherwise be incompatible with polymerization conditions, enhancing synthetic efficiency and facilitating the creation of complex polymer architectures for specialized applications, such as biomedical devices, electronics, and advanced coatings. Herein, we report a method inspired by late-stage functionalization of small molecules for the post-polymerization modification of aromatic polymers, specifically polystyrene (PS), under mild reaction conditions. First, PS was converted to polystyrene sulfonamide (PSSNH 2 ) with an 85% yield using established procedures. PSSNH 2 was subsequently transformed into a reactive sulfinate by deamination using an N-heterocyclic carbene (NHC) catalyst and benzaldehyde. The catalytic process was optimized by varying catalysts, solvents, bases, temperatures, and reaction times. The highest degree of deamination was 88% with a bicyclic NHC and K 2 CO 3 base in DMSO for 18 hours at 120 °C. The reactive sulfinate was then treated with various functional reagents, resulting in a library of aromatic polymers with different substituents with high degrees of functionalization ranging from 74% to 98%. Similarly, we modified expanded PS waste with trifluorobutyl iodide with a degree of functionalization of 72%, highlighting a new avenue for plastic upgrading. This approach could be used to rapidly generate functionalized polymers from PS with potential applications, including antibacterial properties and flame retardancy.

Shrestha, Tulaja [Univ. of Delaware, Newark, DE (U↗
DOE OSTI2022

Activated relaxation in supercooled monodisperse atomic and polymeric WCA fluids: Simulation and ECNLE theory

Here, we combine simulation and Elastically Collective Nonlinear Langevin Equation (ECNLE) theory to study the activated relaxation in monodisperse atomic and polymeric Weeks–Chandler–Andersen (WCA) liquids over a wide range of temperatures and densities in the supercooled regime under isochoric conditions. By employing novel crystal-avoiding simulations, metastable equilibrium dynamics is probed in the absence of complications associated with size polydispersity. Based on a highly accurate structural input from integral equation theory, ECNLE theory is found to describe well the simulated density and temperature dependences of the alpha relaxation time of atomic fluids using a single system-specific parameter, a c , that reflects the nonuniversal relative importance of local cage and collective elastic barriers. For polymer fluids, the explicit dynamical effect of local chain connectivity is modeled at the fundamental dynamic free energy trajectory level based on a different parameter, N c , that quantifies the degree of intramolecular correlation of bonded segment activated barrier hopping. For the flexible chain model studied, a physically intuitive value of N c ≈ 2 results in good agreement between simulation and theory. A direct comparison between atomic and polymeric systems reveals that chain connectivity can speed up activated segmental relaxation due to weakening of equilibrium packing correlations but can slow down relaxation due to local bonding constraints. The empirical thermodynamic scaling idea for the alpha time is found to work well at high densities or temperatures but fails when both density and temperature are low. The rich and subtle behaviors revealed from simulation for atomic and polymeric WCA fluids are all well captured by ECNLE theory.

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

Photoinduced electronic excitations drive polymerization of carbon monoxide: A first-principles study

Under pressure, carbon monoxide (CO) transforms into a polymer that can be recovered to ambient conditions. While this transformation can occur without additional stimuli, experimental observations have shown that laser irradiation can induce a similar transformation at reduced pressure. The resulting polymeric phase, which is metastable under ambient conditions, releases energy through decomposition into more stable configurations. Using time-dependent density functional theory and Born–Oppenheimer molecular dynamics simulations, we investigate the mechanism by which electronic excitation facilitates CO polymerization. Our calculations reveal that electronic excitation enhances carbon–carbon bonding, enabling polymerization at pressures significantly lower than those required by conventional compression methods. In conclusion, these findings suggest that a photo-assisted approach could be employed to synthesize novel, potentially energetic materials under less demanding pressure conditions.

Born-Oppenheimer molecular dynamics↗
DOE OSTI2022

Polymeric multimaterials by photochemical patterning of crystallinity

An organized combination of stiff and elastic domains within a single material can synergistically tailor bulk mechanical properties. However, synthetic methods to achieve such sophisticated architectures remain elusive. We report a rapid, facile, and environmentally benign method to pattern strong and stiff semicrystalline phases within soft and elastic matrices using stereo-controlled ring-opening metathesis polymerization of an industrial monomer, cis -cyclooctene. Dual polymerization catalysis dictates polyolefin backbone chemistry, which enables patterning of compositionally uniform materials with seamless stiff and elastic interfaces. Visible light–induced activation of a metathesis catalyst results in the formation of semicrystalline trans polyoctenamer rubber, outcompeting the formation of cis polyoctenamer rubber, which occurs at room temperature. This bottom-up approach provides a method for manufacturing polymeric materials with promising applications in soft optoelectronics and robotics.

Science & Technology - Other Topics↗
DOE OSTI2021

Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

36 MATERIALS SCIENCE↗
DOE OSTI2025

Videos of Chemically Activated Frontal Polymerization of Thermosets

Video recordings of the frontal ring-opening metathesis polymerization (FROMP) of thermoset polymer specimens in 10mm glass test tubes were collected in order to measure the front speed resulting from varied front initiation methods. Maximum front temperature was also measured. Polymerization resins comprised of dicyclopentadiene (DCPD) with 5 wt% 5-ethylidene-2-norbornene (ENB) added, grubbs’ second generation catalyst, and tributyl phosphite (TBP) inhibitor (8000:1:1 monomer:initiator:inhibitor ratio). Polymerization fronts were triggered using concentrated solutions of grubbs’ third generation catalyst in various solvents.

Cramblitt, Anna C.↗
DOE OSTI2025

Durability and Accelerated Aging Test of the Polymeric Mirror-Film Prototype (CRADA Final Report)

The participant is developing a low-cost liquid metal coating for concentrated solar power (CSP) polymeric mirrors. Current CSP technology uses bulky and costly glass mirrors. As a lighter alternative, polymeric mirror film is cheaper than glass mirrors, yet expensive to manufacture. The participant is working to develop a room temperature liquid-metal thin-film deposition technique and CSP polymeric mirror film that will reduce expenditures by 80% and film cost by 50%.

14 SOLAR ENERGY↗
DOE OSTI2023

Polymeric Membranes for H2S and CO2 Removal from Natural Gas for Hydrogen Production: A Review

Natural gas, an important source of hydrogen, is expected to be crucial in the transition to a hydrogen-based economy. The landscape of the gas processing industry is set to change in the near future with the development of highly acidic sour gas wells. Natural gas purification constitutes a major share of the gas separation membrane market, and the shift to low-quality sour gas wells has been mirrored in the trends of membrane material research. Purification also constitutes the major portion of the cost of natural gas, posing implications for the cost of hydrogen production. This review provides an update on the current state of research regarding polymeric membranes for H2S removal, along with CO2 separation, from natural gas that is used for hydrogen production via steam methane reforming. The challenges of adapting polymeric membranes to ternary H2S/CO2/CH4 separations are discussed in detail. Key polymeric materials are highlighted, and the prospects for their application in H2S removal from natural gas are evaluated. Finally, the growing interest in H2 production from H2S is discussed. Advances in the membrane industry and the emergence of new membrane materials may significantly improve the commercial viability of such processes.

Rao, Shraavya↗
NASA NTRS1971

Hydrocarbon polymeric binder for advanced solid propellant

Various experimental factors were examined to determine the source of difficulty in an isoprene polymerization in the 5-gallon reactor which gave a non-uniform product of low functionality. It was concluded that process improvements relating to initiator and monomer purity were desirable, but that the main difficulty was in the initiator feed system. A new pumping system was installed and an analog simulation of the reactor, feed system and initiator decomposition kinetics was devised which permits the selection of initial initiator concentrations and feed rates to use to give a nearly uniform initiator concentration throughout a polymerization run. An isoprene polymerization was run in which the process improvements were implemented.

Potts, J. E.↗
NASA NTRS1971

Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

Jackson, T. A.↗
NASA NTRS1975

On-line mass spectrometric monitoring of the polymerization of a phenolic-resin-based material

Polymerization of phenolic-resin-based materials requires elevated temperatures. The low thermal conductivity of these materials has led to the use of dielectric heating techniques in lieu of standard convection oven heating to obtain a satisfactory cure. The curing rate and therefore the quality of the cured material depends on the heating rate and maximum temperature attained, parameters which are extremely difficult to measure in dielectric heating units. The dielectric curing of these materials was monitored by using a mass spectrometer to measure the partial pressure of phenol in the gas evolved during polymerization. The resulting plots of phenol partial pressure as a function of time have a characteristic shape, and these may be used to indicate the attainment of complete curing. The validity of the mass spectrometric technique was confirmed by chemical analysis of the polymerized samples.

Aikens, D. A.↗